Flexible DMRG-Based Framework for Anharmonic Vibrational Calculations
OPEN ACCESS
Loading...
Author / Producer
Date
2023-12-26
Publication Type
Journal Article
ETH Bibliography
yes
Citations
Altmetric
OPEN ACCESS
Data
Rights / License
Abstract
We present a novel formulation of the vibrational density matrix renormalization group (vDMRG) algorithm tailored to strongly anharmonic molecules described by general, high-dimensional model representations of potential energy surfaces. For this purpose, we extend the vDMRG framework to support vibrational Hamiltonians expressed in the so-called n-mode second-quantization formalism. The resulting n-mode vDMRG method offers full flexibility with respect to both the functional form of the PES and the choice of the single-particle basis set. We leverage this framework to apply, for the first time, vDMRG based on an anharmonic modal basis set optimized with the vibrational self-consistent field algorithm on an on-the-fly constructed PES. We also extend the n-mode vDMRG framework to include excited-state-targeting algorithms in order to efficiently calculate anharmonic transition frequencies. We demonstrate the capabilities of our novel n-mode vDMRG framework for methyloxirane, a challenging molecule with 24 coupled vibrational modes.
Permanent link
Publication status
published
External links
Editor
Book title
Journal / series
Volume
19 (24)
Pages / Article No.
9329 - 9343
Publisher
American Chemical Society
Event
Edition / version
Methods
Software
Geographic location
Date collected
Date created
Subject
Organisational unit
03736 - Reiher, Markus / Reiher, Markus