Quasi-relativistic approach to analytical gradients of parity violating potentials

Abstract

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.

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

References in corpus (6)

• Progress toward a first observation of parity violation in chiral molecules by high-resolution laser spectroscopy
• Electron correlation and nuclear charge dependence of parity-violating properties in open-shell diatomic molecules
• A new experiment to test parity symmetry in cold chiral molecules using vibrational spectroscopy
• Measuring molecular parity nonconservation using nuclear magnetic resonance spectroscopy
• Chiral molecules as sensitive probes for direct detection of $\mathcal{P}$-odd cosmic fields
• Parity nonconserving interactions of electrons in chiral molecules with cosmic fields

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• Relativistic and quantum electrodynamics effects on NMR shielding tensors of Tl$X$ ($X$ = H, F, Cl, Br, I, At) molecules
• Laser spectroscopy and CP-violation sensitivity of actinium monofluoride
• Parity violation effects in helical osmocene: theoretical analysis and experimental prospects
• Chiral Pt(Me-BPCH): Synthesis and theoretical investigation of parity violation sensitivity