Th. Weber, E. Riedle, and H. J. Neusser, "Rotationally resolved fluorescence-dip and ion-dip spectra of single rovibronic states of benzene," J. Opt. Soc. Am. B 7, 1875-1883 (1990)
We report fluorescence-dip as well as ion-dip spectra of single rovibronic one-photon states of benzene with a linewidth as narrow as 0.14 cm−1. The selective excitation of the rovibronic states was achieved through the combination of a frequency-doubled pulsed amplified cw dye laser (ΔνUV ≈ 100 MHz) and a collimated molecular beam. The detailed analysis of the dip spectra shows that the observed spectral features correspond to single rovibronic transitions if suitable states are excited. From the spectra, precise harmonic frequencies and anharmonic constants for the S0 state are determined. A hitherto unknown Darling–Dennison resonance of the overtones of ν1 with the 52 state is found.
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G″ for the various rotational states in the 62 vibrational state that can be accessed by means of stimulated emission from a given J′, K′,
rotational level (with Hougen’s quantum number G′) in the 61 vibronic state. G″ does not depend on J″, but it depends on K″ and
as shown. A transition is allowed if G″ equals G′ (ΔG = 0). For details see text.
Table 2
Relative Intensity (HL) and Ground-State Energy (E)a
Rotational State
J″
K″
HL
E
J′ = 4
5
5
−2
2.00
1221.32
K′ = 4
5
3
0
0.04
1221.72
4
5
−2
Not possible
4
3
0
0.40
1219.83
3
5
−2
Not possible
3
3
0
1.56
1218.31
J′ = 4
5
5
0
2.00
1220.21
K′ = 4
5
3
+2
0.04
1221.09
4
5
0
Not possible
4
3
+2
0.40
1219.20
3
5
0
Not possible
3
3
+2
1.56
1217.68
J′ = 4
5
2
−2
0.93
1222.66
K′ = 1
5
0
0
0.89
1222.58
4
2
−2
0.90
1220.76
4
0
0
Not possible
3
2
−2
0.17
1219.24
3
0
0
1.11
1219.16
HL (given by the Hönl–London factor) and E (in cm−1) for all possible rovibronic transitions (ΔJ = 0, ±1, ΔK = ±1) from selected rotational states (denoted by J′, K′, and
) of the 6111 vibronic state to rotational states (denoted by J′ and K″) of the 62 vibrational state. For each combination of J′ and K″, three substrates with
exist, but according to symmetry selection rules (see text) only one of them can be reached from each excited vibronic state. The value of the quantum number
for this state is indicated in the table. J″ would be smaller than K″ for some values of J′, K′, ΔJ and ΔK, and the transition is therefore not possible, as is indicated. The transition from the J′ = 4, K′ = 1,
state to the J″ = 4, K″ = 0 state is not possible for nuclear spin symmetry reasons if a P- or R-branch transition is used for excitation.
Table 3
Summary of Selected Spectroscopic Constants for the S0 State of Benzenea
Summary of spectroscopic constants of the S0 state of benzene relevant to and determined in this work. For nondegenerate vibrational states or the l = 0 substate of a degenerate state the value of ζeff is 0 by definition; for details and definitions see text.
G″ for the various rotational states in the 62 vibrational state that can be accessed by means of stimulated emission from a given J′, K′,
rotational level (with Hougen’s quantum number G′) in the 61 vibronic state. G″ does not depend on J″, but it depends on K″ and
as shown. A transition is allowed if G″ equals G′ (ΔG = 0). For details see text.
Table 2
Relative Intensity (HL) and Ground-State Energy (E)a
Rotational State
J″
K″
HL
E
J′ = 4
5
5
−2
2.00
1221.32
K′ = 4
5
3
0
0.04
1221.72
4
5
−2
Not possible
4
3
0
0.40
1219.83
3
5
−2
Not possible
3
3
0
1.56
1218.31
J′ = 4
5
5
0
2.00
1220.21
K′ = 4
5
3
+2
0.04
1221.09
4
5
0
Not possible
4
3
+2
0.40
1219.20
3
5
0
Not possible
3
3
+2
1.56
1217.68
J′ = 4
5
2
−2
0.93
1222.66
K′ = 1
5
0
0
0.89
1222.58
4
2
−2
0.90
1220.76
4
0
0
Not possible
3
2
−2
0.17
1219.24
3
0
0
1.11
1219.16
HL (given by the Hönl–London factor) and E (in cm−1) for all possible rovibronic transitions (ΔJ = 0, ±1, ΔK = ±1) from selected rotational states (denoted by J′, K′, and
) of the 6111 vibronic state to rotational states (denoted by J′ and K″) of the 62 vibrational state. For each combination of J′ and K″, three substrates with
exist, but according to symmetry selection rules (see text) only one of them can be reached from each excited vibronic state. The value of the quantum number
for this state is indicated in the table. J″ would be smaller than K″ for some values of J′, K′, ΔJ and ΔK, and the transition is therefore not possible, as is indicated. The transition from the J′ = 4, K′ = 1,
state to the J″ = 4, K″ = 0 state is not possible for nuclear spin symmetry reasons if a P- or R-branch transition is used for excitation.
Table 3
Summary of Selected Spectroscopic Constants for the S0 State of Benzenea
Summary of spectroscopic constants of the S0 state of benzene relevant to and determined in this work. For nondegenerate vibrational states or the l = 0 substate of a degenerate state the value of ζeff is 0 by definition; for details and definitions see text.
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