Using computational chemistry to design pump-probe schemes for measuring nitrobenzene radical cation dynamics.

Physical Chemistry Chemical Physics : PCCP
Hugo A López PeñaKatharine Moore Tibbetts

Abstract

The electronic potential energy surfaces of the nitrobenzene cation obtained from time-dependent density functional theory and coupled cluster calculations are used to predict the most efficient excitation wavelength for femtosecond time-resolved mass spectrometry measurements. Both levels of theory identify a strongly-coupled transition from the ground state of the nitrobenzene cation with a geometry-dependent oscillator strength, reaching a maximum at 90° C-C-N-O dihedral angle with a corresponding energy gap of ∼2 eV. These results are consistent with the experimental observation in the nitrobenzene cation of a coherent superposition of vibrational states: a vibrational wave packet. Time-resolved measurements using a probe wavelength of 650 nm, nearly resonant with the strong transition, result in enhanced ion yield oscillation amplitudes as compared to excitation with the nonresonant 800 nm wavelength. Analogous behavior is found for the closely related molecules 2- and 4-nitrotoluene. These results demonstrate that computational chemistry can predict the best choice of probe wavelength in time-resolved measurements of vibrational coherent states in molecular cations.

References

Jan 24, 1998·Nature·T P SnowV M Bierbaum
Jan 3, 2001·Physical Review Letters·M LeziusM Y Ivanov
Apr 5, 2003·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Stefan Grimme, Maja Parac
Oct 9, 2007·The Journal of Chemical Physics·Brett J PearsonThomas Weinacht
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Jeng-Da Chai, Martin Head-Gordon
Nov 28, 2008·Journal of the American Society for Mass Spectrometry·Christopher MullenHarald Oser
Sep 30, 2010·Physical Chemistry Chemical Physics : PCCP·Jesús González-VázquezTamás Rozgonyi
Jan 13, 2011·The Journal of Physical Chemistry. a·Xin ZhuMarcos Dantus
Oct 1, 2011·The Journal of Physical Chemistry. a·Rasmus Y BrogaardTheis I Sølling
Aug 18, 2012·The Journal of Chemical Physics·Raúl MonteroAsier Longarte
Oct 24, 2012·The Journal of Physical Chemistry. a·Raúl MonteroAsier Longarte
Oct 25, 2013·The Journal of Physical Chemistry. a·Timothy BohinskiRobert Levis
Mar 1, 2014·The Journal of Physical Chemistry. a·Katharine Moore TibbettsRobert Levis
Oct 15, 2014·The Journal of Physical Chemistry. a·Arkaprabha KonarMarcos Dantus
Aug 12, 2015·The Journal of Physical Chemistry Letters·Antonio PrljClémence Corminboeuf
Aug 15, 2015·The Journal of Physical Chemistry Letters·Timothy BohinskiRobert J Levis
May 16, 2013·The Journal of Physical Chemistry Letters·Timothy BohinskiRobert J Levis
May 5, 2016·Journal of Chemical Theory and Computation·Antonio PrljClémence Corminboeuf
Dec 15, 2017·Physical Chemistry Chemical Physics : PCCP·Derrick Ampadu BoatengKatharine Moore Tibbetts
Jan 4, 2018·Journal of Chemical Theory and Computation·Atanu AcharyaVictor S Batista
Apr 9, 2018·The Journal of Chemical Physics·Derrick Ampadu BoatengKatharine Moore Tibbetts
Jan 23, 2019·The Journal of Physical Chemistry. a·Derrick Ampadu BoatengKatharine Moore Tibbetts
Jan 31, 2019·Physical Chemistry Chemical Physics : PCCP·James A GreenDmitrii V Shalashilin
Feb 3, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Derrick Ampadu BoatengKatharine Moore Tibbetts
Mar 9, 2019·Physical Chemistry Chemical Physics : PCCP·Timothy D ScarboroughCornelis J G J Uiterwaal
Mar 16, 2019·Chemistry : a European Journal·Katharine Moore Tibbetts

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Citations

Aug 5, 2021·Analytical Chemistry·Shane L McPhersonKatharine Moore Tibbetts

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Software Mentioned

CCSD
Chem
TDDFT
MATLAB
EOM
EE
Gaussian

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