Rotationally resolved electronic spectra of two conformational isomers of jet-cooled indole-4-carboxylic acid (I4CA) and the deuterated forms of the acid (—COOD) and amide (—ND) groups have been obtained using a UV laser/molecular beam spectrometer. The in-plane orientation of the acid group defines the two lowest energy rotamers of I4CA. The S1 ← S0 origin bands of the two rotamers and four isotopologues have been fit to asymmetric rotor Hamiltonians in both electronic states. From the best-fit parameters, the positions of the H-atoms in the principal axis frames of each conformer have been determined and serve to unambiguously identify the syn forms (i.e., COH⋯O) of the cis and trans rotamers. The experimental S0 and S1 inertial parameters, hydrogen atom positions, and transition dipole moment (TDM) orientations are compared with the results of theoretical calculations. The TDM orientation indicates that the S1 state is the 1La state in contrast to most substituted indoles. The molecular orbital properties and natural charges are investigated to better understand the 1La/1Lb state reversal and the extent of photoinduced intramolecular charge transfer that impacts the rotamer-dependent fluorescence lifetimes.
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14 April 2020
Research Article|
April 14 2020
Rotationally resolved UV spectroscopy of the rotamers of indole-4-carboxylic acid: Evidence for charge transfer quenching Available to Purchase
John T. Yi
;
John T. Yi
1
Department of Chemistry, Winston-Salem State University
, Winston-Salem, North Carolina 27110, USA
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S. Romero-Servin;
S. Romero-Servin
2
División de Ciencias e Ingenierías, Universidad de Guanajuato-Campus León
, León, Guanajuato 37150, Mexico
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Leonardo Álvarez-Valtierra
;
Leonardo Álvarez-Valtierra
a)
2
División de Ciencias e Ingenierías, Universidad de Guanajuato-Campus León
, León, Guanajuato 37150, Mexico
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David F. Plusquellic
David F. Plusquellic
a)
3
Molecular and Biophotonics Group, Applied Physics Division, Physical Measurement Laboratory, National Institute of Standards and Technology
, Boulder, Colorado 80305, USA
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John T. Yi
1
S. Romero-Servin
2
Leonardo Álvarez-Valtierra
2,a)
David F. Plusquellic
3,a)
1
Department of Chemistry, Winston-Salem State University
, Winston-Salem, North Carolina 27110, USA
2
División de Ciencias e Ingenierías, Universidad de Guanajuato-Campus León
, León, Guanajuato 37150, Mexico
3
Molecular and Biophotonics Group, Applied Physics Division, Physical Measurement Laboratory, National Institute of Standards and Technology
, Boulder, Colorado 80305, USA
J. Chem. Phys. 152, 144307 (2020)
Article history
Received:
January 30 2020
Accepted:
March 15 2020
Citation
John T. Yi, S. Romero-Servin, Leonardo Álvarez-Valtierra, David F. Plusquellic; Rotationally resolved UV spectroscopy of the rotamers of indole-4-carboxylic acid: Evidence for charge transfer quenching. J. Chem. Phys. 14 April 2020; 152 (14): 144307. https://doi.org/10.1063/5.0003140
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