2D Plot of three lowest 1A′ states (S0, S2, and S3, solid color) with C–Cl distance fixed (rCCl = 1.6 Å). S3 is seen to cross S2 and S0 at θ = 180°, but the crossings are avoided at bent geometries.
Plots (points) of a 1D scan of the S2 potential of CHCl in Jacobi coordinates. Filled symbols correspond to fixed C–H, C–Cl distances, open symbols are fully relaxed. The fully relaxed scan was used to solve the 1D bend Hamiltonian using a Legendre DVR.
Optical-optical double resonance (OODR) spectra of the S2 state of CH35Cl. The broad features represent upward transition to the S2 state, while narrow features reflect downward (SEP) transitions to known vibrational levels of the S0 state.
Optical-optical double resonance (OODR) spectra of the S2 state of CD35Cl. The rotationally resolved spectra in the upper panel were obtained through an intermediate rovibrational level of the S1 state with J = 5 and K a = 0.
Plots of a 5th-order polynomial fit to the calculated (0, n 0, 0) n = 0, 2, …, 18 even progressions matched up with the experimentally observed (0, n 1, 0) n = 3, 5, …, 17 odd progressions for CHCl and CDCl.
Single point energies (in kcal mol−1) of important stationary points on the CHCl potential energy surfaces, computed at MRCI(+Q) level of theory, as discussed in the text, and equilibrium geometries of the transition states. The figures in italics are the (R/U)CCSD(T) energies. Bond lengths are in Å and bond angles are in degrees.
Measured homogeneous linewidths in the S2 states of CD35Cl (upper panel) and CD35Cl plotted as a function of energy above the vibrationless level of S0.
Assignments, energies, rotational constants, and linewidths of all CH35Cl and CD35Cl S2 state vibrational levels measured in this work.
CH35Cl/CD35Cl S2 vibrational parameters determined from the Dunham expansion fit.a
Calculated geometric parameters (Å, degrees) and harmonic frequencies (cm−1) for the S0, S1, S2, and T1 states of H(D)CCl at the MRCI(+Q)/CBS level (see text).
Components of energy gaps between the S0, S1, S2, and T1 states of CHCl and their extrapolation behavior.
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