NMR¶
Contents
For the calculation of NMR spectra with CENSO, the anmr program is needed.
The spectra can be plotted with the python script nrmplot.py. Both programs can be obtained from the latest release page of ENSO:
https://github.com/grimme-lab/enso/releases/tag/v.2.0.2
ANMR¶
ANMR requires the files:
coord, turbomole data group
anmr_nucinfo (human readable), written by crest
information on which nuclei can interchange in your molecule (e.g. the hydrogen atoms in a methlygroup)
= information on chemical and magnetical equivalent atoms
anmr_rotamer (machine readable), written by crest
information on the rotamers detected by crest
anmr_enso, written by censo
information on the contributing conformers, the Boltzmann weight and all contributions to free energy
.anmrrc, written by censo
anmr searches for the .anmrrc file first in the folder of execution and if not found in the home directory of the user
The file contains the reference-shieldings of e.g TMS to convert the calculated shielding to shifts
the folders with the property calculations of the conformers
e.g. CONF1/NMR
Example .anmrrc file:
7 8 XH acid atoms
ENSO qm= TM mf= 300 lw= 1.0 J= on S= on
TMS[chcl3] pbe0[COSMO]/def2-TZVP//pbeh-3c[DCOSMO-RS]/def2-mSVP
1 31.786 0.0 1
6 189.674 0.0 0
9 182.57 0.0 0
15 291.9 0.0 0
The first line in .anmrrc informs anmr to ignore all protons bound to nitrogen
(N=7) and oxygen (O=8). If you want to calculate protons bound to oxygen or nitrogen,
simply remove the corresponding number, but leave the rest of the line intact!
The next line starting with ENSO informs ANMR that the property calculation
was performed by TM = TURBOMOLE (or ORCA = ORCA). The mf= 300 informs ANMR
that the magnetic frequency of the NMR spectrometer is set to 300 MHz. The lw
(linewidth for plotting) is 1.0 and J (couplings) and S (shieldings) are to be evaluated.
If S= off then ANMR will terminate after calculating and averaging the shifts of the
molecule under consideration. The next line explains how the reference shieldings are
calculated: in this case the reference molecule is tetramethylsilane in chloroform and the
shielding is calculated with PBE0/def2-TZVP + COSMO on PBEh-3c + DCOSMO-RS geometries.
The following lines contain the data on [atomic number] [calculated shielding valule of the reference molecule] [experimental shift] [active or not].
The lines show the reference shieldings for hydrogen (1), carbon (6) fluor (9) and phosphorus (15). The third number within the last four lines is 0.0 and can be used to adjust the shift of the reference (e.g. to the experimental shift). The last number in the last four lines can either be 1 or 0 and this switches the ‘element on or off’ for the spectrum calculation.
Example anmr_enso file:
ONOFF NMR CONF BW Energy Gsolv RRHO
1 1 1 0.10042 -354.38939 -0.00899 0.22109
1 2 2 0.32452 -354.39034 -0.00899 0.22093
1 3 3 0.57506 -354.39287 -0.00902 0.22295
The file anmr_enso is written by the censo program and contains information on
the conformers, which folder they are in, the Boltzmann weight, energy, solvation
and thermostatistical contribution to free energy. The first number in the three last
lines indicates to ANMR if the conformer is to be considered (1) or not (0).
If one conformer is not considered (or more) the anmr program internally recalculates
the Boltzmann weights based on the free energies from the anmr_enso file.
Usage of anmr:
Important
ANMR still relies on autmatically created arrays on the stack. For this reason you have to run ulimit -s unlimited to prevent stackoverflows.
$ anmr --help
# explanation of all possible command line arguments
# shown in next tab
+--------------------------------------+
| A N M R |
| S. Grimme |
| Universitaet Bonn, MCTC |
| 1989-2019 |
| version 3.5.1 |
| Sat Feb 9 06:41:57 CET 2019 |
+--------------------------------------+
Based on a TurboPascal program written
in 1989 which was translated to F90 in
2005 and re-activated in 2017.
Please cite work employing this code as:
ANMR Ver. 3.5: An automatic, QC based
coupled NMR spectra simulation program.
S. Grimme, Universitaet Bonn, 2019
S. Grimme, C. Bannwarth, S. Dohm, A. Hansen
J. Pisarek, P. Pracht, J. Seibert, F. Neese
Angew. Chem. Int. Ed. 2017, 56, 14763-14769.
DOI:10.1002/anie.201708266
=============================
# OMP threads = 4
=============================
usage :
anmr [options]
General options:
-tm : use TURBOMOLE J/sigma
-orca : use ORCA J/sigma
-adf : use ADF J/sigma
-gauss : use GAUSSIAN J/sigma
-plain : use plain input for J/sigma
-chk : perform input check
-acid : remove acidic XH protons
-nofrag : no fragmentation
-mfrag : fragmentation type mol
-afrag : fragmentation type at
-mss : maxsspin
-fragss : fragmentation scheme
-mf : magnetic frequency of exp.
-lw : line width of generated spectrum
-ascal : chemical shift scaling a
-bscal : chemical shift scaling b
-cscal : spin-spin coupling scal factor
-nc : number of conformers
-poff : plot offset
-r : range min max [-r <real1> <real2]
-pthr : min population for which NMR data are read
-nl : points for lorentzian for plotting
-onlyshifts : stop after shift averaging
-h : print help
Note
The usage of the -plain option is recommended so that the coupling constants are read from the CONFXX/NMR/nmrprop.dat
file written by CENSO instead of the output files of the used QM program package, whose formatting
often changes with new versions.
First of all: the spin problem is of \(2^{N}\) complexity! Depending on the size of the maximalspinsystem (mss) the program might use a lot of RAM! If this is the case, run anmr with a decreased spinsystem size:
$ anmr -mss 12 -plain > anmr.out 2> anmr.error &
anmr will then write a file called anmr.dat (which is quiet large). The file contains the information ppm vs intesity. This file can then be plotted with any plotting tool or our ‘nmrplot.py’.
To reduce the large size of the file you can remove entries which are close to zero with either this awk or python code:
head -1 anmr.dat > newanmr.dat
awk '($2 > 0.001){print $0}' anmr.dat >> newanmr.dat
tail -1 anmr.dat >> newanmr.dat
import numpy as np
data = np.genfromtxt('anmr.dat')
threshold = 0.001
data2 = data[np.logical_not(data[:,1] < threshold)]
data2 = np.insert(data2, 0, (data[0][0], threshold), axis=0)
data2 = np.insert(data2, len(data2), (data[-1][0], threshold), axis=0)
np.savetxt('newanmr.dat', data2, fmt='%2.5e' )
Spectra Plotting¶
The NMR spectrum can be plotted from the file anmr.dat. It contains the information ppm vs intensity and can be plotted with any plotting tool (e.g GNUPLOT …).
The provided nmrplot.py plotting tool uses matplotlib for plotting. Information on all possible commandline arguments is documented:
$ nmrplot.py --help
__________________________________________________
| |
| NMRPLOT |
| Plotting of NMR spectral data |
| University of Bonn, MCTC |
| January 2019 |
| v 1.05 |
| F. Bohle |
|__________________________________________________|
Information on arguments:
End Endremove Startremove Start
+ + + +
+---------------+----+-------------------------------+
lower field higher field
delta /ppm
optional arguments:
-h, --help show this help message and exit
-start START, --startppm START
Start plotting from '<start>' ppm. (default: 0)
-end END, --endppm END
End plotting at '<end>' ppm. Value of end has to be
larger than value of start. (default: 11)
-startremove STARTREMOVE, --startremove STARTREMOVE
Start cutting from spectrum at '<startremove>' ppm.
(default: None)
-endremove ENDREMOVE, --endremove ENDREMOVE
End cutting from spectrum at '<endremove>' ppm. Value
of endremove has to be larger than value of
startremove. (default: None)
-title TITLE, --title TITLE
Set title of entire plot. If no title is required use
'<--title ''>'. (default: NMR-PLOT)
-lw LINEWIDTH, --linewidth LINEWIDTH
Set linewidth. (default: 0.8)
-i FILE [FILE ...], --input FILE [FILE ...]
Provide input_file(s) [max 3 files] -i input1(theory1)
input2(theory2) input3(experiment/predicition);
inputfiles format is two columns: column1 ppm ,
column2 intensity; if several files are provided the
last one will be inverted (default: None)
-l LABEL [LABEL ...], --label LABEL [LABEL ...]
Provide labels for all files provided [max 3 files] -l
label1 label2 label3, if no labels are provided,
filename is used as label (default: [])
-fontsize FONTSIZE, --fontsize FONTSIZE
Set fontsize for entire plot. (default: 15)
-keybox, --keybox Set Frame around key. (default: False)
-ontop, --ontop Plot all spectra ontop of each other. (default: False)
-stacked, --stacked Plot all spectra stacked over each other. (default:
False)
-orientation ORIENTATION [ORIENTATION ...], --orientation ORIENTATION [ORIENTATION ...]
Up (1) or down (-1). (default: [1, 1, 1, 1, 1, 1, 1,
1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1, 1])
-c [ ...], --colors [ ...]
Select colors. Possible are: ['gray', 'blue', 'cyan',
'red', 'green', 'magenta', 'yellow', 'black']
(default: ['blue', 'black', 'red', 'magenta',
'green'])
-cut CUT [CUT ...], --cut CUT [CUT ...]
Cut intensity. Accepts values from 0.0 (flat line) to
1.0 (full intensity). (default: [1.0, 1.0, 1.0, 1.0,
1.0, 1.0, 1.0, 1.0, 1.0, 1.0, 1.0, 1.0])
-o OUT, --output OUT Provide name of the output file without fileending.
(default: nmrplot)
-s SHIFT [SHIFT ...], --shift SHIFT [SHIFT ...]
Shift ppm of each inputfile separately using: --shift
float float float, e.g. --shift 10.0 0.0 -5.0, each
file needs its own value (default: [])
Reference shielding constants¶
For user convenience shielding constants of the reference molecules (TMS (Tetramethylsilane), CFCl3, PH3, TMP (Trimethylphosphine oxide)) were precalculated (for some method combinations) and stored within the CENSO program. The reference shielding values are used in the ANMR program to calculate the shifts and the reference values are written to the file .anmrrc.
To be consistent with your calculation, the reference shielding values were calculated on the reference molecules with many possible geometry-optimization-settings eg. {TURBOMOLE/ORCA, PBEh-3c / TPSS-D3/def2-TZVP / B97-3c, (gas phase or solvent)}. The shieldings were then calculated either with TPSS or PBE0 and depending on ORCA (gas or SMD and def2-TZVP basis set) or TURBOMOLE (gas or DCOSMO-RS with the def2-TZVP basis set). At the end of part4 the file .anmrrc is written into the calculation folder and stores the reference shielding values of your settings for the subsequent ANMR calculation.
Note
The CENSO program only writes the reference shielding values to the file ‘.anmrrc’ but does not do anything with it. Hence, no results of CENSO are influenced by a non-matching reference value. If you want to change the reference shielding values, you can simply modify the file ‘.anmrrc’ manually before calling the ANMR program.
Procedure for generating the refrence shielding constants: Geometry optimization with the respective reference molecule with PBEh-3c/B97-3c/TPSS-D3/def2-TZVP + implicit solvation model (either SMD or DCOSMO-RS). NMR shielding constant calculation with the respective functional and the def2-TZVP basis set (again with implicit solvation model).
Input structures for the respective reference molecules:
$ cat coord
$coord
2.05833045453195 -2.05833045453195 2.05833045453195 c
3.27901073396930 -3.27901073396930 0.93023223253204 h
3.27901073396930 -0.93023223253204 3.27901073396930 h
0.93023223253204 -3.27901073396930 3.27901073396930 h
-0.00000000000000 0.00000000000000 0.00000000000000 si
-2.05833045453195 2.05833045453195 2.05833045453195 c
-3.27901073396930 3.27901073396930 0.93023223253204 h
-0.93023223253204 3.27901073396930 3.27901073396930 h
-3.27901073396930 0.93023223253204 3.27901073396930 h
2.05833045453195 2.05833045453195 -2.05833045453195 c
0.93023223253204 3.27901073396930 -3.27901073396930 h
3.27901073396930 0.93023223253204 -3.27901073396930 h
3.27901073396930 3.27901073396930 -0.93023223253204 h
-2.05833045453195 -2.05833045453195 -2.05833045453195 c
-3.27901073396930 -3.27901073396930 -0.93023223253204 h
-3.27901073396930 -0.93023223253204 -3.27901073396930 h
-0.93023223253204 -3.27901073396930 -3.27901073396930 h
$end
$ cat coord
$coord
0.00000000000000 0.00000000000000 1.08780842165939 p
1.12108786201329 1.94178113675579 -0.36261095596909 h
1.12108786201329 -1.94178113675579 -0.36261095596909 h
-2.24217572402658 0.00000000000000 -0.36261095596909 h
$end
$ cat coord
$coord
2.10707881159693 -2.37905657209703 -0.95048934768032 c
-0.00002761513490 -0.00001720463363 0.42981024146152 p
0.00022116674358 -0.00003978704989 3.20441724940919 o
-3.11402725504898 -0.63518697865997 -0.95026063129186 c
-4.41578089847492 0.80223353974588 -0.26675109605744 h
-3.74806612133726 -2.46831651344230 -0.26795802048584 h
-3.07053848205114 -0.62555829073221 -3.00039235368914 h
1.00685206250598 3.01430306976026 -0.95039040993479 c
2.90134987179607 3.42432987586201 -0.26440712265899 h
-0.26551500181645 4.47957166601373 -0.27057128439357 h
0.99633316768277 2.97084963842055 -3.00047015163533 h
4.01209383139734 -2.01044112204817 -0.27010522766248 h
1.51433033394466 -4.22477273833643 -0.26505344320048 h
2.07522150306901 -2.34774660838157 -3.00060121737073 h
$end
$ cat coord
$coord
0.00000038126763 -0.00000000884504 0.13419916242803 c
0.00000870296281 0.00000001369727 2.66116007348966 f
3.17274491422955 -0.00000000906271 -0.93176725824334 cl
-1.58637567202181 -2.74767202581384 -0.93179226251812 cl
-1.58637568491745 2.74767203002431 -0.93179224376158 cl
$end
Example calculation for reference shielding constant¶
In this usage example, CENSO printed an error-message that the reference absolute shielding constant at the level of
theory chosen is missing for hydrogen and has not been precalculated.
ERROR: The reference absolute shielding constant for element h could not be found!
You have to edit the file .anmrrc by hand!
To calculate it, a NMR calculation at the respective level of theory has to be performed for TMS in a new directory. In this case, the theory level is PBE0/def2-TZVP for the NMR part on r2SCAN-3c geometries with the implicit SMD solvation model for CHCl3 (PBE0[SMD]/def2-TZVP//r2scan-3c[SMD]/def2-mTZVPP).
$ mkdir tms
$ cd tms
$ cat coord
$coord
2.05833045453195 -2.05833045453195 2.05833045453195 c
3.27901073396930 -3.27901073396930 0.93023223253204 h
3.27901073396930 -0.93023223253204 3.27901073396930 h
0.93023223253204 -3.27901073396930 3.27901073396930 h
-0.00000000000000 0.00000000000000 0.00000000000000 si
-2.05833045453195 2.05833045453195 2.05833045453195 c
-3.27901073396930 3.27901073396930 0.93023223253204 h
-0.93023223253204 3.27901073396930 3.27901073396930 h
-3.27901073396930 0.93023223253204 3.27901073396930 h
2.05833045453195 2.05833045453195 -2.05833045453195 c
0.93023223253204 3.27901073396930 -3.27901073396930 h
3.27901073396930 0.93023223253204 -3.27901073396930 h
3.27901073396930 3.27901073396930 -0.93023223253204 h
-2.05833045453195 -2.05833045453195 -2.05833045453195 c
-3.27901073396930 -3.27901073396930 -0.93023223253204 h
-3.27901073396930 -0.93023223253204 -3.27901073396930 h
-0.93023223253204 -3.27901073396930 -3.27901073396930 h
$end
$ crest coord -gfn2 -alpb chcl3 -T 4 -nmr > crest.out
$ mkdir censo
$ cp crest_conformers.xyz coord anmr_nucinfo anmr_rotamer censo/
$ cd censo/
$ censo --input crest_conformers.xyz -func0 b97-d3 -solvent chcl3 -smgsolv1 smd -sm2 smd
--smgsolv2 smd --prog orca -part4 on -prog4J orca -prog4S orca -funcJ pbe0
-funcS pbe0 -basisJ def2-TZVP -basisS def2-TZVP -cactive off > censo.out
$CENSO global configuration file: .censorc
$VERSION:1.1.2
ORCA: /home/$USER/orca_5_0_1_linux_x86-64_openmpi411
ORCA version: 5.0.1
GFN-xTB: /home/$USER/bin/xtb
CREST: /home/$USER/bin/crest
mpshift: /home/$USER/TURBOMOLE.7.5/bin/em64t-unknown-linux-gnu/mpshift
escf: /home/$USER/TURBOMOLE.7.5/bin/em64t-unknown-linux-gnu/escf
#COSMO-RS
ctd = BP_TZVP_C30_1601.ctd cdir = "/home/$USER/COSMOthermX16/COSMOtherm/CTDATA-FILES" ldir = "/home/$USER/COSMOthermX16/COSMOtherm/CTDATA-FILES"
$ENDPROGRAMS
$CRE SORTING SETTINGS:
$GENERAL SETTINGS:
nconf: all # ['all', 'number e.g. 10 up to all conformers']
charge: 0 # ['number e.g. 0']
unpaired: 0 # ['number e.g. 0']
solvent: gas # ['gas', 'acetone', 'acetonitrile', 'aniline', 'benzaldehyde', 'benzene', 'ccl4', '...']
prog_rrho: xtb # ['xtb']
temperature: 298.15 # ['temperature in K e.g. 298.15']
trange: [273.15, 378.15, 5] # ['temperature range [start, end, step]']
multitemp: on # ['on', 'off']
evaluate_rrho: on # ['on', 'off']
consider_sym: on # ['on', 'off']
bhess: on # ['on', 'off']
imagthr: automatic # ['automatic or e.g., -100 # in cm-1']
sthr: automatic # ['automatic or e.g., 50 # in cm-1']
scale: automatic # ['automatic or e.g., 1.0 ']
rmsdbias: off # ['on', 'off']
sm_rrho: alpb # ['alpb', 'gbsa']
progress: off # possibilities
check: on # ['on', 'off']
prog: tm # ['tm', 'orca']
func: r2scan-3c # ['b3-lyp', 'b3lyp', 'b3lyp-3c', 'b3lyp-d3', 'b3lyp-d3(0)', 'b3lyp-d4', 'b3lyp-nl', '...']
basis: automatic # ['automatic', 'def2-TZVP', 'def2-mSVP', 'def2-mSVP', 'def2-mSVP', 'def2-mSVP', '...']
maxthreads: 7 # ['number of threads e.g. 2']
omp: 4 # ['number cores per thread e.g. 4']
balance: off # possibilities
cosmorsparam: automatic # ['automatic', '12-fine', '12-normal', '13-fine', '13-normal', '14-fine', '...']
$PART0 - CHEAP-PRESCREENING - SETTINGS:
part0: on # ['on', 'off']
func0: b97-d # ['b3-lyp', 'b3lyp', 'b3lyp-3c', 'b3lyp-d3', 'b3lyp-d3(0)', 'b3lyp-d4', '...']
basis0: def2-SV(P) # ['automatic', 'def2-SV(P)', 'def2-TZVP', 'def2-mSVP', 'def2-mSVP', 'def2-mSVP', '...']
part0_gfnv: gfn2 # ['gfn1', 'gfn2', 'gfnff']
part0_threshold: 4.0 # ['number e.g. 4.0']
$PART1 - PRESCREENING - SETTINGS:
# func and basis is set under GENERAL SETTINGS
part1: on # ['on', 'off']
smgsolv1: cosmors # ['alpb_gsolv', 'cosmo', 'cosmors', 'cosmors-fine', 'cpcm', 'dcosmors', '...']
part1_gfnv: gfn2 # ['gfn1', 'gfn2', 'gfnff']
part1_threshold: 3.5 # ['number e.g. 5.0']
$PART2 - OPTIMIZATION - SETTINGS:
# func and basis is set under GENERAL SETTINGS
part2: on # ['on', 'off']
opt_limit: 2.5 # ['number e.g. 4.0']
sm2: default # ['cosmo', 'cpcm', 'dcosmors', 'default', 'smd']
smgsolv2: cosmors # ['alpb_gsolv', 'cosmo', 'cosmors', 'cosmors-fine', 'cpcm', 'dcosmors', '...']
part2_gfnv: gfn2 # ['gfn1', 'gfn2', 'gfnff']
ancopt: on # ['on']
hlow: 0.01 # ['lowest force constant in ANC generation, e.g. 0.01']
opt_spearman: on # ['on', 'off']
part2_threshold: 99 # ['Boltzmann sum threshold in %. e.g. 95 (between 1 and 100)']
optlevel2: automatic # ['crude', 'sloppy', 'loose', 'lax', 'normal', 'tight', 'vtight', 'extreme', '...']
optcycles: 8 # ['number e.g. 5 or 10']
spearmanthr: -4.0 # ['value between -1 and 1, if outside set automatically']
radsize: 10 # ['number e.g. 8 or 10']
crestcheck: off # ['on', 'off']
$PART3 - REFINEMENT - SETTINGS:
part3: off # ['on', 'off']
prog3: prog # ['tm', 'orca', 'prog']
func3: pw6b95 # ['b3-lyp', 'b3lyp', 'b3lyp-3c', 'b3lyp-d3', 'b3lyp-d3(0)', 'b3lyp-d4', 'b3lyp-nl', '...']
basis3: def2-TZVPD # ['DZ', 'QZV', 'QZVP', 'QZVPP', 'SV(P)', 'SVP', 'TZVP', 'TZVPP', 'aug-cc-pV5Z', '...']
smgsolv3: cosmors # ['alpb_gsolv', 'cosmo', 'cosmors', 'cosmors-fine', 'cpcm', 'dcosmors', '...']
part3_gfnv: gfn2 # ['gfn1', 'gfn2', 'gfnff']
part3_threshold: 99 # ['Boltzmann sum threshold in %. e.g. 95 (between 1 and 100)']
$NMR PROPERTY SETTINGS:
$PART4 SETTINGS:
part4: off # ['on', 'off']
couplings: on # ['on', 'off']
progJ: prog # ['tm', 'orca', 'adf', 'prog']
funcJ: PBE0 # ['b3-lyp', 'b3lyp', 'b3lyp-3c', 'b3lyp-d3', 'b3lyp-d3(0)', 'b3lyp-d4', 'b3lyp-nl', '...']
basisJ: def2-TZVP # ['DZ', 'QZV', 'QZVP', 'QZVPP', 'SV(P)', 'SVP', 'TZVP', 'TZVPP', 'aug-cc-pV5Z', '...']
sm4J: default # ['cosmo', 'cpcm', 'dcosmors', 'smd']
shieldings: on # ['on', 'off']
progS: prog # ['tm', 'orca', 'adf', 'prog']
funcS: PBE0 # ['b3-lyp', 'b3lyp', 'b3lyp-3c', 'b3lyp-d3', 'b3lyp-d3(0)', 'b3lyp-d4', 'b3lyp-nl', '...']
basisS: def2-TZVP # ['DZ', 'QZV', 'QZVP', 'QZVPP', 'SV(P)', 'SVP', 'TZVP', 'TZVPP', 'aug-cc-pV5Z', '...']
sm4S: default # ['cosmo', 'cpcm', 'dcosmors', 'smd']
reference_1H: TMS # ['TMS']
reference_13C: TMS # ['TMS']
reference_19F: CFCl3 # ['CFCl3']
reference_29Si: TMS # ['TMS']
reference_31P: TMP # ['TMP', 'PH3']
1H_active: on # ['on', 'off']
13C_active: on # ['on', 'off']
19F_active: off # ['on', 'off']
29Si_active: off # ['on', 'off']
31P_active: off # ['on', 'off']
resonance_frequency: 300.0 # ['MHz number of your experimental spectrometer setup']
$OPTICAL ROTATION PROPERTY SETTINGS:
$PART5 SETTINGS:
optical_rotation: off # ['on', 'off']
funcOR: pbe # ['functional for opt_rot e.g. pbe']
funcOR_SCF: r2scan-3c # ['functional for SCF in opt_rot e.g. r2scan-3c']
basisOR: def2-SVPD # ['basis set for opt_rot e.g. def2-SVPD']
frequency_optical_rot: [589.0] # ['list of freq in nm to evaluate opt rot at e.g. [589, 700]']
$END CENSORC
______________________________________________________________
| |
| |
| CENSO - Commandline ENSO |
| v 1.1.2 |
| energetic sorting of CREST Conformer Rotamer Ensembles |
| University of Bonn, MCTC |
| Feb 2021 |
| based on ENSO version 2.0.1 |
| F. Bohle and S. Grimme |
| |
|______________________________________________________________|
Please cite:
S. Grimme, F. Bohle, A. Hansen, P. Pracht, S. Spicher, and M. Stahn
J. Phys. Chem. A 2021, 125, 19, 4039-4054.
DOI: https://doi.org/10.1021/acs.jpca.1c00971
This program is distributed in the hope that it will be useful,
but WITHOUT ANY WARRANTY; without even the implied warranty of
MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE.
----------------------------------------------------------------------------------------------------
PARAMETERS
----------------------------------------------------------------------------------------------------
program call: censo --input crest_conformers.xyz -func0 b97-d3 -solvent chcl3 -smgsolv1 smd -sm2 smd --smgsolv2 smd --prog orca -part4 on -prog4J orca -prog4S orca -funcJ pbe0 -funcS pbe0 -basisJ def2-TZVP -basisS def2-TZVP
The configuration file .censorc is read from /home/$USER/.censorc.
Reading conformer rotamer ensemble from: /tmp1/$USER/3881229.majestix.thch.uni-bonn.de/crest_conformers.xyz.
Reading file: censo_solvents.json
--------------------------------------------------
CRE SORTING SETTINGS
--------------------------------------------------
number of atoms in system: 17
number of considered conformers: 2
number of all conformers from input: 2
charge: 0
unpaired: 0
solvent: chcl3
temperature: 298.15
evaluate at different temperatures: on
temperature range: 273.15, 278.15, 283.15, 288.15, ...
calculate mRRHO contribution: on
consider symmetry for mRRHO contribution: on
cautious checking for error and failed calculations: on
checking the DFT-ensemble using CREST: off
maxthreads: 7
omp: 4
automatically balance maxthreads and omp: off
--------------------------------------------------
CRE CHEAP-PRESCREENING - PART0
--------------------------------------------------
part0: on
starting number of considered conformers: 2
program for part0: orca
functional for fast single-point: b97-d3
basis set for fast single-point: def2-SV(P)
threshold g_thr(0) for sorting in part0: 4.0
Solvent model used with xTB: alpb
short-notation:
b97-d3/def2-SV(P) // GFNn-xTB (Input geometry)
--------------------------------------------------
CRE PRESCREENING - PART1
--------------------------------------------------
part1: on
program for part1: orca
functional for initial evaluation: r2scan-3c
basis set for initial evaluation: def2-mTZVPP
calculate mRRHO contribution: on
program for mRRHO contribution: xtb
GFN version for mRRHO and/or GBSA_Gsolv: gfn2
Apply constraint to input geometry during mRRHO calculation: on
solvent model applied with xTB: alpb
evaluate at different temperatures: off
threshold g_thr(1) and G_thr(1) for sorting in part1: 3.5
solvent model for Gsolv contribution of part1: smd
short-notation:
r2scan-3c + SMD[chcl3] + GmRRHO(GFN2[alpb]-bhess) // GFNn-xTB (Input geometry)
--------------------------------------------------
CRE OPTIMIZATION - PART2
--------------------------------------------------
part2: on
program: orca
functional for part2: r2scan-3c
basis set for part2: def2-mTZVPP
using xTB-optimizer for optimization: on
using the new ensemble optimizer: on
optimize all conformers below this G_thr(opt,2) threshold: 2.5
spearmanthr: 0.941
optimization level in part2: lax
solvent model applied in the optimization: smd
solvent model for Gsolv contribution: smd
evaluate at different temperatures: on
Boltzmann sum threshold G_thr(2) for sorting in part2: 99.0
calculate mRRHO contribution: on
program for mRRHO contribution: xtb
GFN version for mRRHO and/or GBSA_Gsolv: gfn2
Apply constraint to input geometry during mRRHO calculation: on
solvent model applied with xTB: alpb
short-notation:
r2scan-3c + SMD[chcl3] + GmRRHO(GFN2[alpb]-bhess) // r2scan-3c[SMD]
--------------------------------------------------
NMR MODE SETTINGS
--------------------------------------------------
part4: on
calculate couplings (J): on
program for coupling calculations: orca
solvation model for coupling calculations: smd
functional for coupling calculation: PBE0
basis set for coupling calculation: def2-TZVP
calculate shieldings (S): on
program for shielding calculations: orca
solvation model for shielding calculations: smd
functional for shielding calculation: PBE0
basis set for shielding calculation: def2-TZVP
Calculating proton spectrum: on
reference for 1H: TMS
resonance frequency: 300.0
END of parameters
------------------------------------------------------------
PATHS of external QM programs
------------------------------------------------------------
The following program paths are used:
ORCA: /tmp1/orca_5_0_1_linux_x86-64_openmpi411
ORCA Version: 5.01
xTB: /home/abt-grimme/AK-bin/xtb
TURBOMOLE: /home/abt-grimme/TURBOMOLE.7.5//bin/em64t-unknown-linux-gnu_smp
Using cefine from /tmp/_MEIaCcz3S/cefine
PARNODES for TM or COSMO-RS calculation was set to 4
----------------------------------------------------------------------------------------------------
Processing data from previous run (enso.json)
----------------------------------------------------------------------------------------------------
INFORMATION: No restart information exists and is created during this run!
----------------------------------------------------------------------------------------------------
CRE CHEAP-PRESCREENING - PART0
----------------------------------------------------------------------------------------------------
program: orca
functional for part0: b97-d3
basis set for part0: def2-SV(P)
threshold g_thr(0): 4.0
starting number of considered conformers: 2
temperature: 298.15
Calculating efficient gas-phase single-point energies:
The efficient gas-phase single-point is calculated for:
CONF1, CONF2
Constructed folders!
Starting 2 ALPB-Gsolv calculations
Running single-point in CONF1/part0_sp
Running single-point in CONF2/part0_sp
Running ALPB_GSOLV calculation in 3881229.majestix.thch.uni-bonn.de/CONF2/part0_sp
Running ALPB_GSOLV calculation in 3881229.majestix.thch.uni-bonn.de/CONF1/part0_sp
Tasks completed!
The efficient gas-phase single-point was successful for CONF1/part0_sp: E(DFT) = -448.78335711 Gsolv = -0.00964593
The efficient gas-phase single-point was successful for CONF2/part0_sp: E(DFT) = -448.78106942 Gsolv = -0.00949351
----------------------------------------------------------------------------------------------------
Removing high lying conformers by improved energy description
----------------------------------------------------------------------------------------------------
CONF# E [Eh] ΔE [kcal/mol] E [Eh] Gsolv [Eh] gtot ΔE(DFT) ΔGsolv Δgtot
GFN2-xTB GFN2-xTB b97-d3/def2-SV(P) alpb [Eh] [kcal/mol] [kcal/mol] [kcal/mol]
[alpb] [alpb] [gfn2]
CONF1 -16.3966231 0.00 -448.7833571 -0.0096459 -448.7930030 0.00 0.00 0.00 <------
CONF2 -16.3954819 0.72 -448.7810694 -0.0094935 -448.7905629 1.44 0.10 1.53
----------------------------------------------------------------------------------------------------
Number of conformers observed within the following Δg windows:
Δg [kcal/mol] #CONF sum(Boltzmann_weights)
---------------------------------------------
0 - 0.5 1 0.93
0 - 1.0 1 0.93
0 - 1.5 1 0.93
0 - 2.0 2 1.00
---------------------------------------------
All relative (free) energies are below the initial g_thr(0) threshold of 4.0 kcal/mol.
All conformers are considered further.
Calculating Boltzmann averaged (free) energy of ensemble on input geometries (not DFT optimized)!
temperature /K: avE(T) /a.u. avG(T) /a.u.
----------------------------------------------------------------------------------------------------
298.15 -448.7831966 -448.7928319 <<==part0==
----------------------------------------------------------------------------------------------------
>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>END of Part0<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<
Ran part0 in 4.4449 seconds
----------------------------------------------------------------------------------------------------
CRE PRESCREENING - PART1
----------------------------------------------------------------------------------------------------
program: orca
functional for part1 and 2: r2scan-3c
basis set for part1 and 2: def2-mTZVPP
Solvent: chcl3
solvent model for Gsolv contribution: smd
threshold g_thr(1) and G_thr(1): 3.5
starting number of considered conformers: 2
calculate mRRHO contribution: on
program for mRRHO contribution: xtb
GFN version for mRRHO and/or GBSA_Gsolv: gfn2
Apply constraint to input geometry during mRRHO calculation: on
temperature: 298.15
Calculating single-point energies and solvation contribution (G_solv):
The prescreening_single-point is calculated for:
CONF1, CONF2
Constructed folders!
Running single-point in CONF1/r2scan-3c
Running single-point in CONF2/r2scan-3c
Tasks completed!
prescreening_single-point calculation was successful for CONF1/r2scan-3c: -449.11349203
prescreening_single-point calculation was successful for CONF2/r2scan-3c: -449.11143980
--------------------------------------------------
Removing high lying conformers
--------------------------------------------------
CONF# E(GFNn-xTB) ΔE(GFNn-xTB) E [Eh] Gsolv [Eh] gtot Δgtot
[a.u.] [kcal/mol] r2scan-3c incl. in E [Eh] [kcal/mol]
[SMD]
CONF1 -16.3952414 0.00 -449.1134920 0.0000000 -449.1134920 0.00 <------
CONF2 -16.3940994 0.72 -449.1114398 0.0000000 -449.1114398 1.29
All relative (free) energies are below the g_thr(1) threshold of 3.5 kcal/mol.
All conformers are considered further.
--------------------------------------------------
Calculating prescreening G_mRRHO with implicit solvation!
The prescreening G_mRRHO calculation is now performed for:
CONF1, CONF2
Constructed folders!
Starting 2 G_RRHO calculations.
Running GFN2-xTB mRRHO in CONF1/rrho_part1
Running GFN2-xTB mRRHO in CONF2/rrho_part1
WARNING: found 1 significant imaginary frequencies in CONF2/rrho_part1
Tasks completed!
The prescreening G_mRRHO run @ td was successful for CONF1/rrho_part1: 0.11573915 S_rot(sym)= 0.0023462 using= 0.1157391
The prescreening G_mRRHO run @ c3v was successful for CONF2/rrho_part1: 0.11540064 S_rot(sym)= 0.0010373 using= 0.1154006
--------------------------------------------------
* Gibbs free energies of part1 *
--------------------------------------------------
CONF# G(GFNn-xTB) ΔG(GFNn-xTB) E [Eh] Gsolv [Eh] GmRRHO [Eh] Gtot ΔGtot
[a.u.] [kcal/mol] r2scan-3c incl. in E GFN2 [Eh] [kcal/mol]
[SMD] [alpb]-bhess
CONF1 -16.2795022 0.00 -449.1134920 0.0000000 0.1157391 -448.9977529 0.00 <------
CONF2 -16.2786988 0.50 -449.1114398 0.0000000 0.1154006 -448.9960392 1.08
Number of conformers observed within the following ΔG windows:
ΔG [kcal/mol] #CONF sum(Boltzmann_weights)
---------------------------------------------
0 - 0.5 1 0.86
0 - 1.0 1 0.86
0 - 1.5 2 1.00
---------------------------------------------
Additional global 'fuzzy-threshold' based on the standard deviation of (G_mRRHO):
Std_dev(G_mRRHO) = 0.150 kcal/mol
Fuzzythreshold = 0.107 kcal/mol
Final sorting threshold G_thr(1) = 3.500 + 0.107 = 3.607 kcal/mol
Spearman correlation coefficient between (E + Solv) and (E + Solv + mRRHO) = 1.000
All relative (free) energies are below the initial G_thr(1) threshold of 3.5 kcal/mol.
All conformers are considered further.
Calculating Boltzmann averaged free energy of ensemble on input geometries (not DFT optimized)!
temperature /K: avE(T) /a.u. avGmRRHO(T) /a.u. avGsolv(T) /a.u. avG(T) /a.u.
----------------------------------------------------------------------------------------------------
298.15 -449.1132047 0.1156917 0.0000000 -448.9975129 <<==part1==
----------------------------------------------------------------------------------------------------
Calculating unbiased GFNn-xTB energy
Constructed folders!
Starting 2 xTB - single-point calculations.
gfn2-xTB energy for CONF1/GFN_unbiased = -16.3966231
gfn2-xTB energy for CONF2/GFN_unbiased = -16.3954819
Tasks completed!
>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>END of Part1<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<
Ran part1 in 9.1081 seconds
----------------------------------------------------------------------------------------------------
CRE OPTIMIZATION - PART2
----------------------------------------------------------------------------------------------------
program: orca
functional for part2: r2scan-3c
basis set for part2: def2-mTZVPP
using the xTB-optimizer for optimization: on
using the new ensemble optimizer: on
optimize all conformers below this G_thr(opt,2) threshold: 2.5
Spearman threshold: 0.941
number of optimization iterations: 8
radsize: 10
optimization level in part2: lax
solvent: chcl3
solvent model applied in the optimization: smd
solvent model for Gsolv contribution: smd
temperature: 298.15
evalulate at different temperatures: on
temperature range: 273.15, 278.15, 283.15, 288.15, ...
Boltzmann sum threshold G_thr(2) for sorting in part2: 99.0
calculate mRRHO contribution: on
program for mRRHO contribution: xtb
GFN version for mRRHO and/or GBSA_Gsolv: gfn2
Apply constraint to input geometry during mRRHO calculation: on
Optimizing geometries at DFT level with implicit solvation!
The optimization is calculated for:
CONF1, CONF2
Constructed folders!
Preparing 2 calculations.
Tasks completed!
************************Starting optimizations************************
Starting threshold is set to 2.5 + 60.0 % = 4.0 kcal/mol
Lower limit is set to G_thr(opt,2) = 2.5 kcal/mol
*******************************CYCLE 1********************************
Starting 2 optimizations.
Running optimization in CONF1/r2scan-3c
Running optimization in CONF2/r2scan-3c
Tasks completed!
Geometry optimization converged for: CONF1 within 3 cycles
Geometry optimization converged for: CONF2 within 3 cycles
Constructed folders!
Starting 2 G_RRHO calculations.
Running GFN2-xTB mRRHO in r2scan-3c/rrho_crude
Running GFN2-xTB mRRHO in r2scan-3c/rrho_crude
Tasks completed!
The G_mRRHO calculation on crudely optimized DFT geometry @ td was successful for CONF1/r2scan-3c/rrho_crude: 0.1157450 S_rot(sym)= 0.0023462 using= 0.1157450
The G_mRRHO calculation on crudely optimized DFT geometry @ c3v was successful for CONF2/r2scan-3c/rrho_crude: 0.1146578 S_rot(sym)= 0.0010373 using= 0.1146578
***********************Finished optimizations!************************
Timings:
Cycle: [s] #nconfs Spearman coeff.
1 34.85 2
sum: 34.85
CONVERGED optimizations for the following remaining conformers:
Converged optimization for CONF1 after 3 cycles: -449.1155065
Converged optimization for CONF2 after 3 cycles: -449.1133322
Calculating single-point energies and solvation contribution (G_solv)!
CONF1, CONF2
Running single-point in CONF1/r2scan-3c
Running single-point in CONF2/r2scan-3c
Tasks completed!
lowlevel single-point calculation was successful for CONF1/r2scan-3c: -449.11550627
lowlevel single-point calculation was successful for CONF2/r2scan-3c: -449.11333157
Calculating lowlevel G_mRRHO with implicit solvation on DFT geometry!
The lowlevel G_mRRHO calculation is now performed for:
CONF1, CONF2
Constructed folders!
Starting 2 G_RRHO calculations.
Running GFN2-xTB mRRHO in CONF1/rrho_part2
Running GFN2-xTB mRRHO in CONF2/rrho_part2
Tasks completed!
The lowlevel G_mRRHO calculation @ td was successful for CONF1/rrho_part2: 0.11574502 S_rot(sym)= 0.0023462 using= 0.1157450
The lowlevel G_mRRHO calculation @ c3v was successful for CONF2/rrho_part2: 0.11465779 S_rot(sym)= 0.0010373 using= 0.1146578
--------------------------------------------------
* Gibbs free energies of part2 *
--------------------------------------------------
CONF# E(GFNn-xTB) ΔE(GFNn-xTB) E [Eh] Gsolv [Eh] GmRRHO [Eh] Gtot ΔGtot Boltzmannweight
[a.u.] [kcal/mol] r2scan-3c incl. in E GFN2 [Eh] [kcal/mol] % at 298.15 K
[SMD] [alpb]-bhess
CONF1 -16.3952414 0.00 -449.1155063 0.0000000 0.1157450 -448.9997612 0.00 75.98 <------
CONF2 -16.3940994 0.72 -449.1133316 0.0000000 0.1146578 -448.9986738 0.68 24.02
Number of conformers observed within the following ΔG windows:
ΔG [kcal/mol] #CONF sum(Boltzmann_weights)
---------------------------------------------
0 - 0.5 1 0.76
0 - 1.0 2 1.00
---------------------------------------------
Calculating Boltzmann averaged free energy of ensemble!
temperature /K: avE(T) /a.u. avGmRRHO(T) /a.u. avGsolv(T) /a.u. avG(T) /a.u.
----------------------------------------------------------------------------------------------------
273.15 -449.1150651 0.1190010 0.0000000 -448.9960641
278.15 -449.1150486 0.1183075 0.0000000 -448.9967412
283.15 -449.1150323 0.1176087 0.0000000 -448.9974236
288.15 -449.1150158 0.1169054 0.0000000 -448.9981104
293.15 -449.1149998 0.1161973 0.0000000 -448.9988025
298.15 -449.1149840 0.1154839 0.0000000 -448.9995001 <<==part2==
303.15 -449.1149681 0.1147661 0.0000000 -449.0002020
308.15 -449.1149528 0.1140434 0.0000000 -449.0009094
313.15 -449.1149376 0.1133166 0.0000000 -449.0016210
318.15 -449.1149227 0.1125847 0.0000000 -449.0023381
323.15 -449.1149077 0.1118481 0.0000000 -449.0030596
328.15 -449.1148932 0.1111069 0.0000000 -449.0037863
333.15 -449.1148790 0.1103615 0.0000000 -449.0045175
338.15 -449.1148646 0.1096115 0.0000000 -449.0052531
343.15 -449.1148509 0.1088570 0.0000000 -449.0059939
348.15 -449.1148374 0.1080973 0.0000000 -449.0067401
353.15 -449.1148237 0.1073340 0.0000000 -449.0074897
358.15 -449.1148107 0.1065661 0.0000000 -449.0082446
363.15 -449.1147975 0.1057936 0.0000000 -449.0090039
368.15 -449.1147853 0.1050171 0.0000000 -449.0097682
373.15 -449.1147730 0.1042360 0.0000000 -449.0105370
----------------------------------------------------------------------------------------------------
--------------------------------------------------
Conformers considered further
--------------------------------------------------
Conformers that are below the Boltzmann threshold G_thr(2) of 99.0%:
CONF1, CONF2
>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>END of Part2<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<
Ran part2 in 39.8941 seconds
----------------------------------------------------------------------------------------------------
NMR MODE - PART4
----------------------------------------------------------------------------------------------------
calculate coupling constants: on
prog4J - program for coupling constant calculation: orca
funcJ - functional for coupling constant calculation: PBE0
basisJ - basis for coupling constant calculation: def2-TZVP
sm4J - solvent model for the coupling calculation: smd
calculate shielding constants σ: on
prog4S - program for shielding constant calculation: orca
funcS - functional for shielding constant calculation: PBE0
basisS - basis for shielding constant calculation: def2-TZVP
sm4S - solvent model for the shielding calculation: smd
Calculating proton spectrum: on
reference for 1H: TMS
spectrometer frequency: 300.0
Considering the following 2 conformers:
CONF1, CONF2
--------------------------------------------------
* Gibbs free energies used in part4 *
--------------------------------------------------
CONF# E [Eh] Gsolv [Eh] GmRRHO [Eh] Gtot ΔGtot Boltzmannweight
r2scan-3c incl. in E GFN2 [Eh] [kcal/mol] % at 298.15 K
[SMD] [alpb]-bhess
CONF1 -449.1155063 0.0000000 0.1157450 -448.9997612 0.00 75.98 <------
CONF2 -449.1133316 0.0000000 0.1146578 -448.9986738 0.68 24.02
Conformers that are below the Boltzmann-thr of 99.0:
CONF1, CONF2
Constructed folders!
Performing coupling constant calculations:
Starting 2 coupling constants calculations
Running coupling calculation in CONF1/NMR
Running coupling calculation in CONF2/NMR
Tasks completed!
Coupling constant calculation was successful for CONF1/NMR
Coupling constant calculation was successful for CONF2/NMR
Performing shielding constant calculations:
Starting 2 shielding constants calculations
Running shielding calculation in CONF1/NMR
Running shielding calculation in CONF2/NMR
Tasks completed!
Shielding constant calculation was successful for CONF1/NMR
Shielding constant calculation was successful for CONF2/NMR
Generating file anmr_enso for processing with the ANMR program.
Writing .anmrrc!
ERROR: The reference absolute shielding constant for element h could not be found!
You have to edit the file .anmrrc by hand!
INFORMATION: The KeyError is: 'r2scan-3c'
Generating plain nmrprop.dat files for each populated conformer.
These files contain all calculated shielding and coupling constants.
The files can be read by ANMR using the keyword '-plain'.
Tasks completed!
Averaged shielding constants:
# in coord element σ(sigma) SD(σ based on SD Gsolv) SD(σ by 0.4 kcal/mol) shift σ_ref
---------------------------------------------------------------------------------------------------------
2 h 31.59 0.000000 0.002263 -31.59 0.000
3 h 31.59 0.000000 0.002263 -31.59 0.000
4 h 31.59 0.000000 0.002263 -31.59 0.000
7 h 31.59 0.000000 0.002263 -31.59 0.000
8 h 31.59 0.000000 0.002263 -31.59 0.000
9 h 31.59 0.000000 0.002263 -31.59 0.000
11 h 31.59 0.000000 0.002263 -31.59 0.000
12 h 31.59 0.000000 0.002263 -31.59 0.000
13 h 31.59 0.000000 0.002263 -31.59 0.000
15 h 31.59 0.000000 0.002263 -31.59 0.000
16 h 31.59 0.000000 0.002263 -31.59 0.000
17 h 31.59 0.000000 0.002263 -31.59 0.000
---------------------------------------------------------------------------------------------------------
# in coord element σ(sigma) min(σ)* CONFX max(σ)* CONFX Δ(max-min)
---------------------------------------------------------------------------------------------------------
2 h 31.59 31.58 CONF2 31.60 CONF1 0.01
3 h 31.59 31.58 CONF2 31.60 CONF1 0.01
4 h 31.59 31.58 CONF2 31.60 CONF1 0.01
7 h 31.59 31.58 CONF2 31.60 CONF1 0.01
8 h 31.59 31.58 CONF2 31.60 CONF1 0.01
9 h 31.59 31.58 CONF2 31.60 CONF1 0.01
11 h 31.59 31.58 CONF2 31.60 CONF1 0.01
12 h 31.59 31.58 CONF2 31.60 CONF1 0.01
13 h 31.59 31.58 CONF2 31.60 CONF1 0.01
15 h 31.59 31.58 CONF2 31.60 CONF1 0.01
16 h 31.59 31.58 CONF2 31.60 CONF1 0.01
17 h 31.59 31.58 CONF2 31.60 CONF1 0.01
---------------------------------------------------------------------------------------------------------
* min(σ) and max(σ) are averaged over the chemical equivalent atoms, but not Boltzmann weighted.
>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>END of Part4<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<
Ran part4 in 66.5507 seconds
Part : #conf time time (including restarts)
-----------------------------------------------------------------------
Input : 2 - -
Part0_all : 2 4.44 s 4.44 s
Part1_initial_sort : 2 8.03 s 8.03 s
Part1_all : 2 9.11 s 9.11 s
Part2_opt : 2 34.85 s 34.85 s
Part2_all : 2 39.89 s 39.89 s
Part4 : 2 66.55 s 66.55 s
-----------------------------------------------------------------------
All parts : - 120.00 s 120.00 s
CENSO all done!
The calculated shift has now to be inserted into the .anmrrc file of the NMR-calculation for the respective molecule:
$ cat .anmrrc
7 8 XH acid atoms
ENSO qm= ORCA mf= 300.0 lw= 1.0 J= on S= on T= 298.15
TMS[chcl3] PBE0[SMD]/def2-TZVP//r2scan-3c[SMD]/def2-mTZVPP
1 31.59 0.0 1