Density Functional Computations of Vibrational Circular Dichroism Spectra beyond the Born-Oppenheimer Approximation
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00524103" target="_blank" >RIV/61388963:_____/20:00524103 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.jctc.0c00081" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jctc.0c00081</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jctc.0c00081" target="_blank" >10.1021/acs.jctc.0c00081</a>
Alternative languages
Result language
angličtina
Original language name
Density Functional Computations of Vibrational Circular Dichroism Spectra beyond the Born-Oppenheimer Approximation
Original language description
Transition-metal complexes provide rich features in vibrational circular dichroism (VCD) spectra, including significant intensity enhancements, and become thus useful in structural and functional studies of molecules. Quite often, however, the vibrational spectral bands are mixed with the electronic ones, and interpretation of such experiments is difficult. In the present study, we elaborate on the theory needed to calculate the VCD intensities beyond the Born-Oppenheimer (BO) approximation. Within a perturbation approach, the coupling between the electronic and vibrational states is estimated using the harmonic approximation and simplified wave functions obtainable from common density functional theory (DFT) computations. Explicit expressions, including Slater determinants and derivatives of molecular orbitals, are given. On a model diamine complex, the implementation is tested and factors affecting spectral intensities and frequencies are investigated. For two larger molecules, the results are in a qualitative agreement with previous experimental data. Typically, the electronic-vibrational interaction Hamiltonian coupling elements are rather small (similar to 0 to 10 cm(-1)), which provides negligible contributions to vibrational frequencies and absorption intensities. However, significant changes in VCD spectra are induced due to the large transition magnetic dipole moment associated with the d-d metal transitions. The possibility to model the spectra beyond the BO limit opens the way to further applications of chiral spectroscopy and transition-metal complexes.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Chemical Theory and Computation
ISSN
1549-9618
e-ISSN
—
Volume of the periodical
16
Issue of the periodical within the volume
4
Country of publishing house
US - UNITED STATES
Number of pages
8
Pages from-to
2627-2634
UT code for WoS article
000526313000052
EID of the result in the Scopus database
2-s2.0-85083544706