Calculation of Quadrupole Coupling Constants: From Gas to Liquid

The effect of hydrogen bonding on the thermodynamic and spectroscopic properties of molecular clusters and liquids

“…For water we calculated a liquid association shift of about 41.2 kHz compared to measured 53 kHz (gas: 308 kHz, 35 liquid: 255 kHz 29 ). Using a combination of ab initio calculations and molecular dynamics simulations Huber 32,33 obtained a value of 252 kHz in excellent agreement with experimental data. For ammonia we obtained a gas to liquid shift of about 14.0 kHz which is smaller than shifts calculated from measured gas (282 kHz, 36 290.6 kHz 37 ) and liquid (232 kHz, 38 245 kHz 39 ) phase data.…”

“…In particular, a direct measurement of the dqcc in the liquid phase is not possible. However, there exist different experimental [29][30][31] and theoretical techniques [32][33][34] for obtaining Fig. 7 (a) Liquid association shift of the proton chemical shifts in water, ammonia, hydrogen sulfide and phosphine.…”

The deuterium quadrupole coupling constant in liquid ammonia

“…Using several experimental and calculated results, Huber obtains approximately 40 Hz K~1 for water. 46 The temperature dependence in ammonia is smaller if the e †ective distance is increased upon cooling, cf. eqns.…”