The spectrum of hot water: Rotational transitions and difference bands in the (020), (100), and (001) vibrational states

TY - JOUR

T1 - The spectrum of hot water: Rotational transitions and difference bands in the (020), (100), and (001) vibrational states

AU - Polyansky, O L

AU - Tennyson, J

AU - Bernath, P F

PY - 1997/12

Y1 - 1997/12

N2 - Analysis of the hot H(2)(16)0 spectrum, presented by Polyansky et al. (1996, J. Mol. Spectrosc. 176, 305-315), is extended to higher vibrational states. Three hundred thirty mainly strong lines are assigned to pure rotational transitions in the (100), (001), and (020) vibrational states. These lines, which involve significantly higher rotational energy levels than were known previously, are assigned using high-accuracy variational calculations. Transitions in (020) are assigned up to K-a = 18, compared with the maximum K-a of 10 known previously. Crossings of vibration-rotation energy levels result in the observation of extra intensity-stealing transitions. In particular, this leads to the assignment of (020)-(100) and(100)-(020) rotational difference band transitions in addition to the conventional pure rotational lines in (020) and (100) states. These extra lines increase the number of transitions and they are likely to complicate the pure rotational water spectrum in higher excited vibrational states to an even greater extent. A few lines from our previous work on the pure rotational spectrum of hot water in the (000) and (010) vibrational states are also reassigned and some further assignments are made. (C) 1997 Academic Press.

AB - Analysis of the hot H(2)(16)0 spectrum, presented by Polyansky et al. (1996, J. Mol. Spectrosc. 176, 305-315), is extended to higher vibrational states. Three hundred thirty mainly strong lines are assigned to pure rotational transitions in the (100), (001), and (020) vibrational states. These lines, which involve significantly higher rotational energy levels than were known previously, are assigned using high-accuracy variational calculations. Transitions in (020) are assigned up to K-a = 18, compared with the maximum K-a of 10 known previously. Crossings of vibration-rotation energy levels result in the observation of extra intensity-stealing transitions. In particular, this leads to the assignment of (020)-(100) and(100)-(020) rotational difference band transitions in addition to the conventional pure rotational lines in (020) and (100) states. These extra lines increase the number of transitions and they are likely to complicate the pure rotational water spectrum in higher excited vibrational states to an even greater extent. A few lines from our previous work on the pure rotational spectrum of hot water in the (000) and (010) vibrational states are also reassigned and some further assignments are made. (C) 1997 Academic Press.

KW - POTENTIAL-ENERGY SURFACE

KW - GROUND-STATE

KW - (H2O)-O-16

KW - APPROXIMATION

KW - CLUSTERS

M3 - Article

VL - 186

SP - 213

EP - 221

JO - JOURNAL OF MOLECULAR SPECTROSCOPY

JF - JOURNAL OF MOLECULAR SPECTROSCOPY

SN - 0022-2852

IS - 2

ER -