Details
| Original language | English |
|---|---|
| Pages (from-to) | 2616-2627 |
| Number of pages | 12 |
| Journal | Journal of Physical Chemistry A |
| Volume | 124 |
| Issue number | 13 |
| Early online date | 3 Mar 2020 |
| Publication status | Published - 2 Apr 2020 |
| Externally published | Yes |
Abstract
We employ and combine a number of recent developments in vibrational structure methods to push their current size limitations toward molecules with tens of modes and showcase their availability for the maleimide molecule. In particular, we assess the use of different rectilinear vibrational coordinates, namely, normal coordinates, hybrid optimized and localized coordinates, and flexible adaptation of local coordinates of nuclei coordinates. These different coordinate parameterizations are employed in conjunction with the adaptive density-guided approach to generate potential energy surfaces (PESs). A screening procedure is furthermore introduced, which provides estimates of the importance of individual terms in the PES, resulting in significant reductions in the computational cost of the PES construction. We find that all three sets of coordinates provide approximately the same level of accuracy in vibrational structure calculations and report fundamental excitation energies with a mean absolute deviation of less than 12 cm -1 when compared to experimental data. We expect that similar accuracy in vibrational structure calculations can be achieved for molecules of larger size using the proposed procedures.
ASJC Scopus subject areas
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Journal of Physical Chemistry A, Vol. 124, No. 13, 02.04.2020, p. 2616-2627.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Toward Accurate Theoretical Vibrational Spectra: A Case Study for Maleimide
AU - Klinting, E.L.
AU - Christiansen, O.
AU - König, Carolin
N1 - Funding information: O.C. acknowledges support from the Danish e-infrastructure Cooperation (DeiC) and the Danish Council for Independent Research through a Sapere Aude III Grant (no. DFF-4002-00015). C.K. acknowledges support from the Deutsche Forschungsgemeinschaft (DFG) through the Emmy Noether Young Group Leader Programme (project KO 5423/1-1).
PY - 2020/4/2
Y1 - 2020/4/2
N2 - We employ and combine a number of recent developments in vibrational structure methods to push their current size limitations toward molecules with tens of modes and showcase their availability for the maleimide molecule. In particular, we assess the use of different rectilinear vibrational coordinates, namely, normal coordinates, hybrid optimized and localized coordinates, and flexible adaptation of local coordinates of nuclei coordinates. These different coordinate parameterizations are employed in conjunction with the adaptive density-guided approach to generate potential energy surfaces (PESs). A screening procedure is furthermore introduced, which provides estimates of the importance of individual terms in the PES, resulting in significant reductions in the computational cost of the PES construction. We find that all three sets of coordinates provide approximately the same level of accuracy in vibrational structure calculations and report fundamental excitation energies with a mean absolute deviation of less than 12 cm -1 when compared to experimental data. We expect that similar accuracy in vibrational structure calculations can be achieved for molecules of larger size using the proposed procedures.
AB - We employ and combine a number of recent developments in vibrational structure methods to push their current size limitations toward molecules with tens of modes and showcase their availability for the maleimide molecule. In particular, we assess the use of different rectilinear vibrational coordinates, namely, normal coordinates, hybrid optimized and localized coordinates, and flexible adaptation of local coordinates of nuclei coordinates. These different coordinate parameterizations are employed in conjunction with the adaptive density-guided approach to generate potential energy surfaces (PESs). A screening procedure is furthermore introduced, which provides estimates of the importance of individual terms in the PES, resulting in significant reductions in the computational cost of the PES construction. We find that all three sets of coordinates provide approximately the same level of accuracy in vibrational structure calculations and report fundamental excitation energies with a mean absolute deviation of less than 12 cm -1 when compared to experimental data. We expect that similar accuracy in vibrational structure calculations can be achieved for molecules of larger size using the proposed procedures.
UR - http://www.scopus.com/inward/record.url?scp=85082979022&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.9b11915
DO - 10.1021/acs.jpca.9b11915
M3 - Article
VL - 124
SP - 2616
EP - 2627
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 13
ER -