Simulation of Vibrational Circular Dichroism Spectra Using Second-Order Møller-Plesset Perturbation Theory and Configuration Interaction Doubles

• URL: http://arxiv.org/abs/2406.05196v1
• Date: Fri, 7 Jun 2024 18:25:24 GMT
• Title: Simulation of Vibrational Circular Dichroism Spectra Using Second-Order Møller-Plesset Perturbation Theory and Configuration Interaction Doubles
• Authors: Brendan M. Shumberger, T. Daniel Crawford,
• Abstract summary: We present the first single-reference calculations of the atomic axial tensors (AATs) using wave-function-based methods. For our molecular test set, we observed deviations of the AATs for MP2 and CID upwards of 49%, varying with the choice of basis set. The inclusion of dynamic electron correlation to the perturbation of the AATs can have a significant impact on the resulting rotatory strengths and VCD spectra.
• Score: 0.0
• License: http://arxiv.org/licenses/nonexclusive-distrib/1.0/
• Abstract: We present the first single-reference calculations of the atomic axial tensors (AATs) using wave-function-based methods including dynamic electron correlation effects using second-order M{\o}ller-Plesset perturbation theory (MP2) and configuration interaction doubles (CID). Our implementation involves computing the overlap of numerical derivatives of the correlated wave functions with respect to both nuclear displacement coordinates and the external magnetic field. Out test set included three small molecules, including the axially chiral hydrogen molecule dimer and (P)-hydrogen peroxide, and the achiral H2O. For our molecular test set, we observed deviations of the AATs for MP2 and CID from that of the Hartree-Fock (HF) method upwards of 49%, varying with the choice of basis set. For (P)-hydrogen peroxide, electron correlation effects on the VCD rotatory strengths and corresponding spectra were particularly significant, with maximum deviations of the rotatory strengths of 62% and 49% for MP2 and CID, respectively, using our largest basis set. The inclusion of dynamic electron correlation to the computation of the AATs can have a significant impact on the resulting rotatory strengths and VCD spectra.

Related papers

• Simulating decoherence of coupled two spin qubits using generalized cluster correlation expansion [2.7354851983299784]
  We study the coherence of two coupled spin qubits in the presence of a bath of nuclear spins. In our model, two electron spin qubits coupled with isotropic exchange or magnetic dipolar interactions interact with an environment of random nuclear spins.
  arXiv  Detail & Related papers  (2024-02-28T21:46:32Z)
• Quantum vibronic effects on the electronic properties of molecular crystals [0.0]
  We consider a system composed of relatively rigid molecules, a diamondoid crystal, and one composed of floppier molecules, NAI-DMAC. We compute fundamental electronic gaps at the DFT level of theory, with the PBE and SCAN functionals, by coupling first-principles molecular dynamics with a nuclear quantum thermostat.
  arXiv  Detail & Related papers  (2023-04-26T17:13:14Z)
• Simulating Spin-Orbit Coupling With Quasidegenerate N-Electron Valence Perturbation Theory [77.34726150561087]
  We present the first implementation of spin-orbit coupling effects in SO-QDNEVPT2. The accuracy of these methods is tested for the group 14 and 16 hydrides, 3d and 4d transition metal ions, and two actinide dioxides.
  arXiv  Detail & Related papers  (2022-11-11T20:03:37Z)
• Molecular formations and spectra due to electron correlations in three-electron hybrid double-well qubits [0.0]
  Wigner molecules (WMs) form in three-electron hybrid qubits based on GaAs asymmetric double quantum dots. FCI calculations enable prediction of the energy spectra and the intrinsic spatial and spin structures of the many-body wave functions. FCI methodology can be straightforwardly extended to treat valleytronic two-band Si/SiGe hybrid qubits.
  arXiv  Detail & Related papers  (2022-04-05T14:28:14Z)
• Relativistic aspects of orbital and magnetic anisotropies in the chemical bonding and structure of lanthanide molecules [60.17174832243075]
  We study the electronic and ro-vibrational states of heavy homonuclear lanthanide Er2 and Tm2 molecules by applying state-of-the-art relativistic methods. We were able to obtain reliable spin-orbit and correlation-induced splittings between the 91 Er2 and 36 Tm2 electronic potentials dissociating to two ground-state atoms.
  arXiv  Detail & Related papers  (2021-07-06T15:34:00Z)
• Controlled coherent dynamics of [VO(TPP)], a prototype molecular nuclear qudit with an electronic ancilla [50.002949299918136]
  We show that [VO(TPP)] (vanadyl tetraphenylporphyrinate) is a promising system suitable to implement quantum computation algorithms. It embeds an electronic spin 1/2 coupled through hyperfine interaction to a nuclear spin 7/2, both characterized by remarkable coherence.
  arXiv  Detail & Related papers  (2021-03-15T21:38:41Z)
• $\mathcal{P}$,$\mathcal{T}$-odd effects for RaOH molecule in the excited vibrational state [77.34726150561087]
  Triatomic molecule RaOH combines the advantages of laser-coolability and the spectrum with close opposite-parity doublets. We obtain the rovibrational wave functions of RaOH in the ground electronic state and excited vibrational state using the close-coupled equations derived from the adiabatic Hamiltonian.
  arXiv  Detail & Related papers  (2020-12-15T17:08:33Z)
• Effects of Conical Intersections on Hyperfine Quenching of Hydroxyl OH in collision with an ultracold Sr atom [62.60678272919008]
  We report on ultracold collision dynamics of the hydroxyl free-radical OH with Sr atoms leading to quenching of OH hyperfine states. Our quantum-mechanical calculations of this process reveal that quenching is efficient due to anomalous molecular dynamics in the vicinity of the conical intersection.
  arXiv  Detail & Related papers  (2020-06-26T23:27:25Z)
• Dynamical Strengthening of Covalent and Non-Covalent Molecular Interactions by Nuclear Quantum Effects at Finite Temperature [58.999762016297865]
  Nuclear quantum effects (NQE) tend to generate delocalized molecular dynamics. NQE often enhance electronic interactions and, in turn, can result in dynamical molecular stabilization at finite temperature. Our findings yield new insights into the versatile role of nuclear quantum fluctuations in molecules and materials.
  arXiv  Detail & Related papers  (2020-06-18T14:30:29Z)

This list is automatically generated from the titles and abstracts of the papers in this site.

This site does not guarantee the quality of this site (including all information) and is not responsible for any consequences.