Journal of Physical Chemistry A, Vol.120, No.4, 503-506, 2016
Resonance-Enhanced Raman Scattering of Ring-Involved Vibrational Modes in the B-1(2u) Absorption Band of Benzene, Including the Kekule Vibrational Modes nu(9) and nu(10)
Resonance Raman spectroscopy provides much stronger Raman signal levels than its off-resonant counterpart and adds selectivity by excitation tuning. Raman preresonance of benzene has been well studied. On-resonance studies, especially at phonon-allowed absorptions, have received less attention. In this case, we observe resonance of many of the vibration modes associated motion of the carbons in the ring while tuning over the B-1(2u) absorption, including the related nu(9) (CC stretch Herzberg notation, nu(14) Wilson notation) and nu(10) (CH-parallel bend Herzberg notation, nu(15) Wilson notation) vibrational nodes along with the nu(2) (CC-stretch or ring-breathing Herzberg notation, nu(10) Wilson notation) mode and multiples of the nu(18) (CCC-parallel bend Herzberg notation, nu(6) Wilson notation) vibrational mode. The ring-breathing mode is found to mix with the b(2u) modes creating higher frequency composites. Through the use of an optical parametric oscillator (OPO) to tune through the B-1(2u) absorption band of liquid benzene, a stiffening (increase in energy) of the vibrational modes is observed as the excitation:wavelength nears the B-1(2u) absorption peak of the isolated molecule (vapor) phase. The strongest resonance amplitude observed is in the 2 x nu(18) (e(2g)) mode, with nearly twice the intensity of the ring-breathing mode, nu(2) Several overtones and combination modes, especially with nu(2) (a(1g), are also observed to resonate. Raman resonances on phonon allowed excitations are narrow and permit the measurement of vibrations not Raman active in the ground state.