Resolving the anomalous infrared spectrum of the MeCN-HCl molecular cluster using ab Initio molecular dynamics

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Resolving the anomalous infrared spectrum of the MeCN-HCl molecular cluster using ab Initio molecular dynamics. / Bork, Nicolai Christian; Loukonen, Ville; Kjærgaard, Henrik Grum; Vehkamäki, Hanna.

I: Physical Chemistry Chemical Physics, Bind 16, Nr. 45, 2014, s. 24685-24690.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Harvard

Bork, NC, Loukonen, V, Kjærgaard, HG & Vehkamäki, H 2014, 'Resolving the anomalous infrared spectrum of the MeCN-HCl molecular cluster using ab Initio molecular dynamics', Physical Chemistry Chemical Physics, bind 16, nr. 45, s. 24685-24690. https://doi.org/10.1039/c4cp03828b

APA

Bork, N. C., Loukonen, V., Kjærgaard, H. G., & Vehkamäki, H. (2014). Resolving the anomalous infrared spectrum of the MeCN-HCl molecular cluster using ab Initio molecular dynamics. Physical Chemistry Chemical Physics, 16(45), 24685-24690. https://doi.org/10.1039/c4cp03828b

Vancouver

Bork NC, Loukonen V, Kjærgaard HG, Vehkamäki H. Resolving the anomalous infrared spectrum of the MeCN-HCl molecular cluster using ab Initio molecular dynamics. Physical Chemistry Chemical Physics. 2014;16(45):24685-24690. https://doi.org/10.1039/c4cp03828b

Author

Bork, Nicolai Christian ; Loukonen, Ville ; Kjærgaard, Henrik Grum ; Vehkamäki, Hanna. / Resolving the anomalous infrared spectrum of the MeCN-HCl molecular cluster using ab Initio molecular dynamics. I: Physical Chemistry Chemical Physics. 2014 ; Bind 16, Nr. 45. s. 24685-24690.

Bibtex

@article{b2e59a7906e4490e9c5912e15ceee2cf,
title = "Resolving the anomalous infrared spectrum of the MeCN-HCl molecular cluster using ab Initio molecular dynamics",
abstract = "We present a molecular dynamics (MD) based study of the acetonitrile-hydrogen chloride molecular cluster in the gas phase, aimed at resolving the anomalous features often seen in infrared spectra of hydrogen bonded complexes. We find that the infrared spectrum obtained from the Fourier transform of the electric dipole moment autocorrelation function converges very slowly due to the floppy nature of the complex. Even after 55 picoseconds of simulation, significant differences in the modelled and experimental spectrum are seen, likely due to insufficient configurational sampling. Instead, we utilize the MD trajectory for a structural based analysis. We find that the most populated values of the N-H-Cl angle are around 162°. The global minimum energy conformation at 180.0° is essentially unpopulated. We re-model the spectrum by combining population data from the MD simulations with optimizations constraining the N-H-Cl angle. This re-modelled spectrum is in excellent accordance with the experimental spectrum and we conclude that the observed spectral anomaly is due to the dynamics of the N-H-Cl angle.",
author = "Bork, {Nicolai Christian} and Ville Loukonen and Kj{\ae}rgaard, {Henrik Grum} and Hanna Vehkam{\"a}ki",
note = "Correction: http://dx.doi.org/10.1039/C5CP90150B",
year = "2014",
doi = "10.1039/c4cp03828b",
language = "English",
volume = "16",
pages = "24685--24690",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "45",

}

RIS

TY - JOUR

T1 - Resolving the anomalous infrared spectrum of the MeCN-HCl molecular cluster using ab Initio molecular dynamics

AU - Bork, Nicolai Christian

AU - Loukonen, Ville

AU - Kjærgaard, Henrik Grum

AU - Vehkamäki, Hanna

N1 - Correction: http://dx.doi.org/10.1039/C5CP90150B

PY - 2014

Y1 - 2014

N2 - We present a molecular dynamics (MD) based study of the acetonitrile-hydrogen chloride molecular cluster in the gas phase, aimed at resolving the anomalous features often seen in infrared spectra of hydrogen bonded complexes. We find that the infrared spectrum obtained from the Fourier transform of the electric dipole moment autocorrelation function converges very slowly due to the floppy nature of the complex. Even after 55 picoseconds of simulation, significant differences in the modelled and experimental spectrum are seen, likely due to insufficient configurational sampling. Instead, we utilize the MD trajectory for a structural based analysis. We find that the most populated values of the N-H-Cl angle are around 162°. The global minimum energy conformation at 180.0° is essentially unpopulated. We re-model the spectrum by combining population data from the MD simulations with optimizations constraining the N-H-Cl angle. This re-modelled spectrum is in excellent accordance with the experimental spectrum and we conclude that the observed spectral anomaly is due to the dynamics of the N-H-Cl angle.

AB - We present a molecular dynamics (MD) based study of the acetonitrile-hydrogen chloride molecular cluster in the gas phase, aimed at resolving the anomalous features often seen in infrared spectra of hydrogen bonded complexes. We find that the infrared spectrum obtained from the Fourier transform of the electric dipole moment autocorrelation function converges very slowly due to the floppy nature of the complex. Even after 55 picoseconds of simulation, significant differences in the modelled and experimental spectrum are seen, likely due to insufficient configurational sampling. Instead, we utilize the MD trajectory for a structural based analysis. We find that the most populated values of the N-H-Cl angle are around 162°. The global minimum energy conformation at 180.0° is essentially unpopulated. We re-model the spectrum by combining population data from the MD simulations with optimizations constraining the N-H-Cl angle. This re-modelled spectrum is in excellent accordance with the experimental spectrum and we conclude that the observed spectral anomaly is due to the dynamics of the N-H-Cl angle.

U2 - 10.1039/c4cp03828b

DO - 10.1039/c4cp03828b

M3 - Journal article

C2 - 25312587

VL - 16

SP - 24685

EP - 24690

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 45

ER -

ID: 131023065