TY - JOUR

T1 - Tailored anharmonic potential energy surfaces for infrared signatures

AU - Hellmers, Janine Isabel

AU - Czember, Pascal

AU - König, Carolin

N1 - Publisher Copyright: © 2024 The Royal Society of Chemistry.

PY - 2024/12/28

Y1 - 2024/12/28

N2 - Accurately calculated infrared spectra are essential for supporting experimental interpretation, yet full-space anharmonic vibrational structure calculations are only feasible for a limited number of degrees of freedom. Fortunately, characteristic spectroscopic signatures are often dominated by a few key vibrations. We propose a computational protocol specifically tailoring high dimensional anharmonic potential energy surfaces for the accurate and efficient calculation of such spectral signatures with vibrational coupled cluster response theory. Our protocol focuses on the selection of appropriate coordinates for the relevant degrees of freedom and the identification of specific mode-coupling terms for the potential energy surface that require more thorough treatment. This includes applying different levels of electronic structure theory and selecting a restricted set of higher mode-coupling terms (> mode pairs). We validate this protocol on two spectral regions: the fundamental C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O stretching vibrations in uracil and the fundamental OH stretchings in catechol. Our findings indicate that the convergence behaviour towards harmonic frequencies in the so-called FALCON algorithm is an effective indicator for the locality character of the relevant degrees of freedom. We find that the C O stretchings in uracil are better described using normal coordinates, while the description with local FALCON coordinates of the OH-stretching vibrations in catechol showed superior performances in VCC spectra calculations. Overall, our protocol offers valuable guidelines for accurate and efficient anharmonic calculation of vibrational spectral signatures.

AB - Accurately calculated infrared spectra are essential for supporting experimental interpretation, yet full-space anharmonic vibrational structure calculations are only feasible for a limited number of degrees of freedom. Fortunately, characteristic spectroscopic signatures are often dominated by a few key vibrations. We propose a computational protocol specifically tailoring high dimensional anharmonic potential energy surfaces for the accurate and efficient calculation of such spectral signatures with vibrational coupled cluster response theory. Our protocol focuses on the selection of appropriate coordinates for the relevant degrees of freedom and the identification of specific mode-coupling terms for the potential energy surface that require more thorough treatment. This includes applying different levels of electronic structure theory and selecting a restricted set of higher mode-coupling terms (> mode pairs). We validate this protocol on two spectral regions: the fundamental C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O stretching vibrations in uracil and the fundamental OH stretchings in catechol. Our findings indicate that the convergence behaviour towards harmonic frequencies in the so-called FALCON algorithm is an effective indicator for the locality character of the relevant degrees of freedom. We find that the C O stretchings in uracil are better described using normal coordinates, while the description with local FALCON coordinates of the OH-stretching vibrations in catechol showed superior performances in VCC spectra calculations. Overall, our protocol offers valuable guidelines for accurate and efficient anharmonic calculation of vibrational spectral signatures.

UR - http://www.scopus.com/inward/record.url?scp=85210952925&partnerID=8YFLogxK

U2 - 10.1039/d4cp02916j

DO - 10.1039/d4cp02916j

M3 - Article

VL - 26

SP - 29732

EP - 29748

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 48

ER -