Computational methodology study of the optical and thermochemical properties of a molecular photoswitch

Stine Tetzschner Olsen; Jonas Elm; Freja Eilsø Storm; Aske Nørskov Gejl; Anne Schou Hansen; Mia Harring Hansen; Jens Rix Nikolajsen; Mogens Brøndsted Nielsen; Henrik Grum Kjærgaard; Kurt Valentin Mikkelsen

doi:10.1021/jp510678u

Computational methodology study of the optical and thermochemical properties of a molecular photoswitch

Stine Tetzschner Olsen, Jonas Elm, Freja Eilsø Storm, Aske Nørskov Gejl, Anne Schou Hansen, Mia Harring Hansen, Jens Rix Nikolajsen, Mogens Brøndsted Nielsen, Henrik Grum Kjærgaard, Kurt Valentin Mikkelsen

Department of Chemistry

39 Citations (Scopus)

Abstract

We assess how the utilization of different DFT functionals for obtaining the equilibrium geometries and vibrational frequencies affect the description of the thermochemistry and subsequent calculation of the optical properties of a dihydroazulene-vinylheptafulvene photoswitch. The assessment covers nine popular DFT functionals (BLYP, B3LYP, CAM-B3LYP, M06-L, M06, M06-2X, PBE, PBE0, and ωB97X-D) in conjugation with five different Pople style basis sets (6-31+G(d), 6-31++G(d,p), 6-311+G(d), 6-311++G(d,p), and 6-311++G(3df,3pd)). It is identified that only CAM-B3LYP, M06-2X, and PBE0 are able to quantitatively describe the correct trends in the thermochemical properties. The subsequent calculation of the optical properties using the CAM-B3LYP functional shows that there is little difference in whether the CAM-B3LYP, M06-2X, or PBE0 functionals have been used to calculate the equilibrium geometries. Utilizing the identified functionals, we investigate how the number of electron withdrawing cyano substituents influence the thermochemistry and optical properties of the molecular photoswitch.

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	119
Issue number	5
Pages (from-to)	896−904
Number of pages	9
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp510678u
Publication status	Published - 5 Feb 2015

Access to Document

10.1021/jp510678u

Cite this

Olsen, S. T., Elm, J., Storm, F. E., Gejl, A. N., Hansen, A. S., Hansen, M. H., Nikolajsen, J. R., Nielsen, M. B., Kjærgaard, H. G., & Mikkelsen, K. V. (2015). Computational methodology study of the optical and thermochemical properties of a molecular photoswitch. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 119(5), 896−904. https://doi.org/10.1021/jp510678u

Computational methodology study of the optical and thermochemical properties of a molecular photoswitch. / Olsen, Stine Tetzschner; Elm, Jonas; Storm, Freja Eilsø et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 119, No. 5, 05.02.2015, p. 896−904.

Research output: Contribution to journal › Journal article › Research › peer-review

Olsen, ST, Elm, J, Storm, FE, Gejl, AN, Hansen, AS, Hansen, MH, Nikolajsen, JR, Nielsen, MB , Kjærgaard, HG & Mikkelsen, KV 2015, 'Computational methodology study of the optical and thermochemical properties of a molecular photoswitch', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 119, no. 5, pp. 896−904. https://doi.org/10.1021/jp510678u

@article{acbaec39e5d14067a9ce927f22fa90b5,

title = "Computational methodology study of the optical and thermochemical properties of a molecular photoswitch",

abstract = "We assess how the utilization of different DFT functionals for obtaining the equilibrium geometries and vibrational frequencies affect the description of the thermochemistry and subsequent calculation of the optical properties of a dihydroazulene-vinylheptafulvene photoswitch. The assessment covers nine popular DFT functionals (BLYP, B3LYP, CAM-B3LYP, M06-L, M06, M06-2X, PBE, PBE0, and ωB97X-D) in conjugation with five different Pople style basis sets (6-31+G(d), 6-31++G(d,p), 6-311+G(d), 6-311++G(d,p), and 6-311++G(3df,3pd)). It is identified that only CAM-B3LYP, M06-2X, and PBE0 are able to quantitatively describe the correct trends in the thermochemical properties. The subsequent calculation of the optical properties using the CAM-B3LYP functional shows that there is little difference in whether the CAM-B3LYP, M06-2X, or PBE0 functionals have been used to calculate the equilibrium geometries. Utilizing the identified functionals, we investigate how the number of electron withdrawing cyano substituents influence the thermochemistry and optical properties of the molecular photoswitch.",

author = "Olsen, {Stine Tetzschner} and Jonas Elm and Storm, {Freja Eils{\o}} and Gejl, {Aske N{\o}rskov} and Hansen, {Anne Schou} and Hansen, {Mia Harring} and Nikolajsen, {Jens Rix} and Nielsen, {Mogens Br{\o}ndsted} and Kj{\ae}rgaard, {Henrik Grum} and Mikkelsen, {Kurt Valentin}",

year = "2015",

month = feb,

day = "5",

doi = "10.1021/jp510678u",

language = "English",

volume = "119",

pages = "896−904",

journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Computational methodology study of the optical and thermochemical properties of a molecular photoswitch

AU - Olsen, Stine Tetzschner

AU - Elm, Jonas

AU - Storm, Freja Eilsø

AU - Gejl, Aske Nørskov

AU - Hansen, Anne Schou

AU - Hansen, Mia Harring

AU - Nikolajsen, Jens Rix

AU - Nielsen, Mogens Brøndsted

AU - Kjærgaard, Henrik Grum

AU - Mikkelsen, Kurt Valentin

PY - 2015/2/5

Y1 - 2015/2/5

N2 - We assess how the utilization of different DFT functionals for obtaining the equilibrium geometries and vibrational frequencies affect the description of the thermochemistry and subsequent calculation of the optical properties of a dihydroazulene-vinylheptafulvene photoswitch. The assessment covers nine popular DFT functionals (BLYP, B3LYP, CAM-B3LYP, M06-L, M06, M06-2X, PBE, PBE0, and ωB97X-D) in conjugation with five different Pople style basis sets (6-31+G(d), 6-31++G(d,p), 6-311+G(d), 6-311++G(d,p), and 6-311++G(3df,3pd)). It is identified that only CAM-B3LYP, M06-2X, and PBE0 are able to quantitatively describe the correct trends in the thermochemical properties. The subsequent calculation of the optical properties using the CAM-B3LYP functional shows that there is little difference in whether the CAM-B3LYP, M06-2X, or PBE0 functionals have been used to calculate the equilibrium geometries. Utilizing the identified functionals, we investigate how the number of electron withdrawing cyano substituents influence the thermochemistry and optical properties of the molecular photoswitch.

AB - We assess how the utilization of different DFT functionals for obtaining the equilibrium geometries and vibrational frequencies affect the description of the thermochemistry and subsequent calculation of the optical properties of a dihydroazulene-vinylheptafulvene photoswitch. The assessment covers nine popular DFT functionals (BLYP, B3LYP, CAM-B3LYP, M06-L, M06, M06-2X, PBE, PBE0, and ωB97X-D) in conjugation with five different Pople style basis sets (6-31+G(d), 6-31++G(d,p), 6-311+G(d), 6-311++G(d,p), and 6-311++G(3df,3pd)). It is identified that only CAM-B3LYP, M06-2X, and PBE0 are able to quantitatively describe the correct trends in the thermochemical properties. The subsequent calculation of the optical properties using the CAM-B3LYP functional shows that there is little difference in whether the CAM-B3LYP, M06-2X, or PBE0 functionals have been used to calculate the equilibrium geometries. Utilizing the identified functionals, we investigate how the number of electron withdrawing cyano substituents influence the thermochemistry and optical properties of the molecular photoswitch.

U2 - 10.1021/jp510678u

DO - 10.1021/jp510678u

M3 - Journal article

C2 - 25569127

SN - 1089-5639

VL - 119

SP - 896−904

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 5

ER -

Computational methodology study of the optical and thermochemical properties of a molecular photoswitch

Abstract

Access to Document

Fingerprint

Cite this