Quasi-relativistic approach to analytical gradients of parity violating potentials
| Autor: | Sascha A. Brück, Nityananda Sahu, Konstantin Gaul, Robert Berger |
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| Rok vydání: | 2023 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 158 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/5.0141271 |
| Popis: | An analytic gradient approach for the computation of derivatives of parity-violating (PV) potentials with respect to displacements of the nuclei in chiral molecules is described and implemented within a quasirelativistic mean-field framework. Calculated PV potential gradients are utilised for estimating PV frequency splittings between enantiomers in rotational and vibrational spectra of four chiral polyhalomethanes, i.e. CHBrClF, CHClFI, CHBrFI and CHAtFI. Values calculated within the single-mode approximation for the frequency shifts agree well with previously reported theoretical values. The influence of non-separable anharmonic effects (multi-mode effects) on the vibrational frequency shifts, which are readily accessible with the present analytic derivative approach, are estimated for the C--F stretching fundamental of all four molecules and computed for each of the fundamentals in CHBrClF and CHAtFI. Multi-mode effects are found to be significant, in particular for the C--F stretching modes, being for some modes and cases of similar size as the single-mode contribution. Comment: 20 p/8 fig/4 tab/suppl: 26 tab; minor text changes/corr, eqs 2/27 corr; Numer. vals changed slightly per: more consist. use of fin. nucl; same numer. grid for zora/pv oper. matrix elem. and derivs; improved acc. in assem. of DFT grad; tighter conv. crit. in HF at CHClFI(eq); fewer digits; Tab I/II vals from fin. suppl. of ref 40, as prev. earlier version was linked on publ.'s webpage |
| Databáze: | OpenAIRE |
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