Local Bond-Stretch Coordinates for Anharmonic Vibrational Computations

Sebastian Riis Thomsen; Nicolai Machholdt Høyer; Mads Greisen Højlund; Ove Christiansen

doi:10.1021/acs.jpca.4c07704

Local Bond-Stretch Coordinates for Anharmonic Vibrational Computations

Sebastian Riis Thomsen^*, Nicolai Machholdt Høyer^*, Mads Greisen Højlund^*, Ove Christiansen^*

^*Corresponding author af dette arbejde

Institut for Kemi

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

Abstract

The local bond-stretch (LBS) method is presented as a means of obtaining a set of localized, rectilinear vibrational modes. Three variants of the LBS method are considered: pure LBS, projected LBS (pLBS), and orthogonal, projected LBS (opLBS). These variants feature different degrees of localization and different coupling terms in the kinetic energy operator, such that the most localized method (LBS) has the largest number and magnitude of coupling terms, and the least localized (opLBS) has the least coupling terms. The different LBS variants are exemplified in computations on overtone vibrational spectra of water, nitroxyl (chemical formula HNO), formaldehyde, and 1,3-butadiene computed with a vibrational coupled cluster band Lanczos approach. These spectra are calculated using potential energy surfaces (PESs) obtained with the adaptive density-guided approach (ADGA). We observe faster convergence with respect to the coupling level in the PES when using the LBS variants compared to normal coordinates. Among the LBS variants, pLBS and opLBS appear most promising.

Originalsprog	Engelsk
Tidsskrift	The journal of physical chemistry. A
Vol/bind	129
Nummer	15
Sider (fra-til)	3522-3536
Antal sider	15
ISSN	1089-5639
DOI	https://doi.org/10.1021/acs.jpca.4c07704
Status	Udgivet - 17 apr. 2025

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Local Bond-Stretch Coordinates for Anharmonic Vibrational Computations. / Thomsen, Sebastian Riis; Høyer, Nicolai Machholdt; Højlund, Mads Greisen et al.
I: The journal of physical chemistry. A, Bind 129, Nr. 15, 17.04.2025, s. 3522-3536.

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

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AU - Høyer, Nicolai Machholdt

AU - Højlund, Mads Greisen

AU - Christiansen, Ove

PY - 2025/4/17

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N2 - The local bond-stretch (LBS) method is presented as a means of obtaining a set of localized, rectilinear vibrational modes. Three variants of the LBS method are considered: pure LBS, projected LBS (pLBS), and orthogonal, projected LBS (opLBS). These variants feature different degrees of localization and different coupling terms in the kinetic energy operator, such that the most localized method (LBS) has the largest number and magnitude of coupling terms, and the least localized (opLBS) has the least coupling terms. The different LBS variants are exemplified in computations on overtone vibrational spectra of water, nitroxyl (chemical formula HNO), formaldehyde, and 1,3-butadiene computed with a vibrational coupled cluster band Lanczos approach. These spectra are calculated using potential energy surfaces (PESs) obtained with the adaptive density-guided approach (ADGA). We observe faster convergence with respect to the coupling level in the PES when using the LBS variants compared to normal coordinates. Among the LBS variants, pLBS and opLBS appear most promising.

AB - The local bond-stretch (LBS) method is presented as a means of obtaining a set of localized, rectilinear vibrational modes. Three variants of the LBS method are considered: pure LBS, projected LBS (pLBS), and orthogonal, projected LBS (opLBS). These variants feature different degrees of localization and different coupling terms in the kinetic energy operator, such that the most localized method (LBS) has the largest number and magnitude of coupling terms, and the least localized (opLBS) has the least coupling terms. The different LBS variants are exemplified in computations on overtone vibrational spectra of water, nitroxyl (chemical formula HNO), formaldehyde, and 1,3-butadiene computed with a vibrational coupled cluster band Lanczos approach. These spectra are calculated using potential energy surfaces (PESs) obtained with the adaptive density-guided approach (ADGA). We observe faster convergence with respect to the coupling level in the PES when using the LBS variants compared to normal coordinates. Among the LBS variants, pLBS and opLBS appear most promising.

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Local Bond-Stretch Coordinates for Anharmonic Vibrational Computations

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