Molecular dynamics in the isothermal-isobaric ensemble: the requirement of a "shell" molecule. I. Theory and phase-space analysis

Current constant pressure molecular-dynamics (MD) algorithms are not consistent with the recent reformulation of the isothermal-isobaric (NpT) ensemble. The NpT ensemble partition function requires the use of a "shell" molecule to identify uniquely the volume of the system, thereby avoiding the redundant counting of configurations [e.g., G. J. M. Koper and H. Reiss, J. Phys. Chem. 100, 422 (1996); D. S. Corti, Phys. Rev. E, 64, 016128 (2001)]. So far, only the NpT Monte Carlo method has been updated to allow the system volume to be defined by a shell particle [D. S. Corti, Mol. Phys. 100, 1887 (2002)]. A shell particle has yet to be incorporated into MD simulations. The proper modification of the NpT MD algorithm is therefore the subject of this paper. Unlike Andersen's method [H. C. Andersen, J. Chem. Phys. 72, 2384 (1980)] where a piston of unknown mass serves to control the response time of volume fluctuations, the newly proposed equations of motion impose a constant external pressure via the introduction of a shell particle of known mass. Hence, the system itself sets the time scales for pressure and volume fluctuations. The new algorithm is subject to a number of fundamentally rigorous tests to ensure that the equations of motion sample phase space correctly. We also show that the Hoover NpT algorithm [W. G. Hoover, Phys. Rev. A. 31, 1695 (1985); 34, 2499 (1986)] does sample phase correctly, but only when periodic boundary conditions are employed.     

Dynamic shear modulus of glycerol: corrections due to instrument compliance

A recent article by Shi et al. [J. Chem. Phys.123, 174507 (2005)] reports results from mechanical measurements on three simple inorganic glass formers: glycerol, m-toluidine, and sucrose benzoate. The experiments carried out were stress relaxation, aging, and dynamic (all in shear) using a torsional rheometer, an advanced rheometric expansion system (TA Instruments). The original force rebalance transducer (2KFRT) supplied with the system was replaced with a custom-made load cell (Sensotec) that had a capacity of 20 000 g cm in torque and 5000 g in normal force. The replacement of the load cell was done due to the belief that the main source of compliance in this instrument was from the 2KFRT. With this assumption, the authors published their results for the three materials of interest and compared their results with the techniques of Schroter and Donth [J. Chem. Phys.113, 9101 (2000)] for the measurements on glycerol and reported important differences. These differences were disputed by one of the present authors (Schroter), and the present report shows that the results from Schroter and Donth are correct. We show that the reasons have to do with the instrument compliance being greater than originally thought by Shi et al. Here we examine the effects of platen diameter/geometry on the glycerol dynamic moduli, describe a means to correct dynamic data, present a revised comparison of the corrected data with that of Schroter and Donth, and provide a discussion of future work and conclusions.     

A global 12-dimensional ab initio potential energy surface and dynamical studies for the SiH4+H-->SiH3+H2 reaction

A global 12-dimensional ab initio interpolated potential energy surface (PES) for the SiH(4)+H-->SiH(3)+H(2) reaction is presented. The ab initio calculations are based on the unrestricted quadratic configuration interaction treatment with all single and double excitations together with the cc-pVTZ basis set, and the modified Shepard interpolation method of Collins and co-workers [K. C. Thompson et al., J. Chem. Phys. 108, 8302 (1998); M. A. Collins, Theor. Chem. Acc. 108, 313 (2002); R. P. A. Bettens and M. A. Collins, J. Chem. Phys. 111, 816 (1999)] is applied. Using this PES, classical trajectory and variational transition state theory calculations have been carried out, and the computed rate constants are in good agreement with the available experimental data.     

Theoretical interpretation of Grimme's spin-component-scaled second order Møller-Plesset theory

It is shown that spin-component-scaled second order M?ller-Plesset theory proposed by Grimme [J. Chem. Phys. 118, 9095 (2003)] can be interpreted as a two-parameter scaling of the zero order Hamiltonian, a generalization of the approach reported by Feenberg [Phys. Rev. 103, 1116 (1956)].     

Elastic electron scattering by C2F4

Recent measurements [R. Panajotovic, M. Jelisavcic, R. Kajita, T. Tanaka, M. Kitajima, H. Cho, H. Tanaka, and S. J. Buckman, J. Chem. Phys. 121, 4559 (2004)] and calculations [C. Trevisan, A. E. Orel, and T. N. Rescigno, Phys. Rev. A 70, 012704 (2004)] of the elastic electron cross section for C(2)F(4) differ materially from our earlier calculations [C. Winstead and V. McKoy, J. Chem. Phys. 116, 1380 (2002)]. Some of the differences are readily attributed to approximations made in our computations, but an overall difference in cross section magnitude above ca. 10 eV was surprising. Here we report a reexamination of the electron-C(2)F(4) elastic cross section. After eliminating or minimizing various possible sources of error, we continue to predict a substantially larger cross section at higher energies.     

Comment on "Theoretical study of the photoinduced transfer among the ground state and two metastable states in [Fe(CN)5NO]2-" [J. Chem. Phys. 122, 074314 (2005)

We discuss the computational results of the "Theoretical study of the photoinduced transfer among the ground state and two metastable states in [Fe(CN)5NO]2-" [J. Chem. Phys. 122, 074314 (2005)] with respect to our previously reported polarized absorption study on the metastable states SI and SII in Na2[Fe(CN)5NO]2H2O [D. Schaniel, J. Schefer, B. Delley, M. Imlau, and Th. Woike, Phys. Rev. B 66, 085103 (2002)].     

Quasirelativistic theory for the magnetic shielding constant. III. Quasirelativistic second-order Møller-Plesset perturbation theory and its application to tellurium compounds

The quasirelativistic (QR) generalized unrestricted Hartree-Fock method for the magnetic shielding constant [R. Fukuda, M. Hada, and H. Nakatsuji, J. Chem. Phys. 118, 1015 (2003); R. Fukuda, M. Hada, and H. Nakatsuji, J. Chem. Phys.118, 1027 (2003)] has been extended to include the electron correlation effect in the level of the second-order M?ller-Plesset perturbation theory (MP2). We have implemented the energy gradient and finite-perturbation methods to calculate the magnetic shielding constant at the QR MP2 level and applied to the magnetic shielding constants and the NMR chemical shifts of 125Te nucleus in various tellurium compounds. The calculated magnetic shielding constants and NMR chemical shifts well reproduced the experimental values. The relations of the chemical shifts with the natures of ligands, and the tellurium oxidation states were investigated. The chemical shifts in different valence states were explained by the paramagnetic shielding and spin-orbit terms. The tellurium 5p electrons are the dominant origin of the chemical shifts in the Te I and Te II compounds and the chemical shifts were explained by the p-hole mechanism. The tellurium d electrons also play an important role in the chemical shifts of the hypervalent compounds.     

High resolution vacuum ultraviolet emission spectrum of D2: the B' 1Sigmau+-->X 1Sigmag+ band system

In this work, we have extended our previous high resolution study of the vacuum ultraviolet emission spectrum of the D2 molecule [M. Roudjane, et al. J. Chem. Phys. 125, 214305 (2006)] up to 124.2 nm in order to investigate the B' 1Sigmau+-->X 1Sigmag+ band system. The analysis of the spectrum has been carried out by means of a complex spectrum visual identification code IDEN [V. I. Azarov, Phys. Scr. 44, 528 (1991); 48, 656, (1993)] and supported by theoretical calculations using ab initio data [L. Wolniewicz, J. Chem. Phys. 103, 1792 (1995); 99, 1851 (1993); G. Staszewska and L. Wolniewicz, J. Mol. Spectrosc. 212, 208 (2002); L. Wolniewicz and G. Staszewska, 220, 45 (2003)] which provided level energies and transition probabilities. More than 1480 new emission lines have been observed and 109 bands belonging to the B' 1Sigmau+-->X 1Sigmag+ system have been identified between 84.1 and 121.6 nm. Except for the upsilon'-0 bands that were reported in absorption [I. Dabrowski and G. Herzberg, Can. J. Phys. 52, 1110 (1974)], all the upsilon'-upsilon" bands are reported here for the first time. The analysis led to the determination of 111 rovibronic energy levels in the B' 1Sigmau+ state, of which 31 with higher rotational numbers J are new. Observed perturbations are accounted for through a set of coupled equations involving the four excited electronic states B 1Sigmau+, B' 1Sigmau+, C 1Piu, and D 1Piu and including nonadiabatic couplings. The solution of this set provides the percent contribution of these four states to each of the observed rovibronic level.     

On the density scaling of pVT data and transport properties for molecular and ionic liquids

In this work, a general equation of state (EOS) recently derived by Grzybowski et al. [Phys. Rev. E 83, 041505 (2011)] is applied to 51 molecular and ionic liquids in order to perform density scaling of pVT data employing the scaling exponent γ(EOS). It is found that the scaling is excellent in most cases examined. γ(EOS) values range from 6.1 for ammonia to 13.3 for the ionic liquid [C(4)C(1)im][BF(4)]. These γ(EOS) values are compared with results recently reported by us [E. R. López, A. S. Pensado, M. J. P. Comu?as, A. A. H. Pádua, J. Fernández, and K. R. Harris, J. Chem. Phys. 134, 144507 (2011)] for the scaling exponent γ obtained for several different transport properties, namely, the viscosity, self-diffusion coefficient, and electrical conductivity. For the majority of the compounds examined, γ(EOS) > γ, but for hexane, heptane, octane, cyclopentane, cyclohexane, CCl(4), dimethyl carbonate, m-xylene, and decalin, γ(EOS) < γ. In addition, we find that the γ(EOS) values are very much higher than those of γ for alcohols, pentaerythritol esters, and ionic liquids. For viscosities and the self-diffusion coefficient-temperature ratio, we have tested the relation linking EOS and dynamic scaling parameters, proposed by Paluch et al. [J. Phys. Chem. Lett. 1, 987-992 (2010)] and Grzybowski et al. [J. Chem. Phys. 133, 161101 (2010); Phys. Rev. E 82, 013501 (2010)], that is, γ = (γ(EOS)/φ) + γ(G), where φ is the stretching parameter of the modified Avramov relation for the density scaling of a transport property, and γ(G) is the Gru?neisen constant. This relationship is based on data for structural relaxation times near the glass transition temperature for seven molecular liquids, including glass formers, and a single ionic liquid. For all the compounds examined in our much larger database the ratio (γ(EOS)/φ) is actually higher than γ, with the only exceptions of propylene carbonate and 1-methylnaphthalene. Therefore, it seems the relation proposed by Paluch et al. applies only in certain cases, and is really not generally applicable to liquid transport properties such as viscosities, self-diffusion coefficients or electrical conductivities when examined over broad ranges of temperature and pressure.     

Communication: Linear-expansion shooting techniques for accelerating self-consistent field convergence

Based on the corrected Hohenberg-Kohn-Sham total energy density functional [Y. A. Zhang and Y. A. Wang, J. Chem. Phys. 130, 144116 (2009)], we have developed two linear-expansion shooting techniques (LIST)- direct LIST (LISTd) and indirect LIST (LISTi), to accelerate the convergence of self-consistent field (SCF) calculations. Case studies show that overall LISTi is the most robust and efficient algorithm for accelerating SCF convergence, whereas LISTd is advantageous in the early stage of an SCF process. More importantly, LISTi outperforms Pulay's direct inversion in the iterative subspace (DIIS) [P. Pulay, J. Comput. Chem. 3, 556 (1982)] and its two recent improvements, energy-DIIS [K. N. Kudin, G. E. Scuseria, and E. Cance?s, J. Chem. Phys. 116, 8255 (2002)] and augmented Roothaan-Hall energy-DIIS [X. Hu and W. Yang, J. Chem. Phys. 132, 054109 (2010)].     

State-to-state rotational transitions in H2+H2 collisions at low temperatures

We present quantum mechanical close-coupling calculations of collisions between two hydrogen molecules over a wide range of energies, extending from the ultracold limit to the superthermal region. The two most recently published potential energy surfaces for the H(2)-H(2) complex, the so-called Diep-Johnson (DJ) [J. Chem. Phys. 112, 4465 (2000); 113, 3480 (2000)] and Boothroyd-Martin-Keogh-Peterson (BMKP) [J. Chem. Phys. 116, 666 (2002)] surfaces, are quantitatively evaluated and compared through the investigation of rotational transitions in H(2)+H(2) collisions within rigid rotor approximation. The BMKP surface is expected to be an improvement, approaching chemical accuracy, over all conformations of the potential energy surface compared to previous calculations of H(2)-H(2) interaction. We found significant differences in rotational excitation/deexcitation cross sections computed on the two surfaces in collisions between two para-H(2) molecules. The discrepancy persists over a large range of energies from the ultracold regime to thermal energies and occurs for several low-lying initial rotational levels. Good agreement is found with experiment B. Mate et al., [J. Chem. Phys. 122, 064313 (2005)] for the lowest rotational excitation process, but only with the use of the DJ potential. Rate coefficients computed with the BMKP potential are an order of magnitude smaller.     

Communication: rationale for a new class of double-hybrid approximations in density-functional theory

We provide a rationale for a new class of double-hybrid approximations introduced by Bre?mond and Adamo [J. Chem. Phys. 135, 024106 (2011)] which combine an exchange-correlation density functional with Hartree-Fock exchange weighted by λ and second-order M?ller-Plesset (MP2) correlation weighted by λ(3). We show that this double-hybrid model can be understood in the context of the density-scaled double-hybrid model proposed by Sharkas et al. [J. Chem. Phys. 134, 064113 (2011)], as approximating the density-scaled correlation functional E(c)[n(1/λ)] by a linear function of λ, interpolating between MP2 at λ = 0 and a density-functional approximation at λ = 1. Numerical results obtained with the Perdew-Burke-Ernzerhof density functional confirms the relevance of this double-hybrid model.     

Electronic structure and spectrum of UO2 2+ and UO2Cl4 2-

A theoretical study is presented of the electronic spectra of the UO(2) (2+) and UO(2)Cl(4) (2-) ions, based on multiconfigurational perturbation theory (CASSCF/CASPT2), combined with a recently developed method to treat spin-orbit coupling [P.-A. Malmqvist et al., Chem. Phys. Lett. 357, 230 (2002); B. O. Roos and P.-A. Malmqvist, Phys. Chem. Chem. Phys. 6, 2919 (2004)]. The results are compared to the experimental spectroscopic data obtained for uranyl ions in Cs(2)UO(2)Cl(4) crystals from Denning [Struct. Bonding (Berlin) 79, 215 (1992)] and to previous theoretical calculations performed using a combined configuration-interaction spin-orbit treatment [Z. Zhang and R. M. Pitzer, J. Phys. Chem. A 103, 6880 (1999); S. Matsika and R. M. Pitzer, J. Phys. Chem. A. 105, 637 (2001)]. As opposed to the latter results, the calculations performed in this work point to a significant effect of the weakly bound equatorial chlorine ligands on the excitation energies.     

Computation of methodology-independent single-ion solvation properties from molecular simulations. IV. Optimized Lennard-Jones interaction parameter sets for the alkali and halide ions in water

The raw single-ion solvation free energies computed from atomistic (explicit-solvent) simulations are extremely sensitive to the boundary conditions and treatment of electrostatic interactions used during these simulations. However, as shown recently [M. A. Kastenholz and P. H. Hu?nenberger, J. Chem. Phys. 124, 224501 (2006); M. M. Reif and P. H. Hu?nenberger, J. Chem. Phys. 134, 144103 (2010)], the application of appropriate correction terms permits to obtain methodology-independent results. The corrected values are then exclusively characteristic of the underlying molecular model including in particular the ion-solvent van der Waals interaction parameters, determining the effective ion size and the magnitude of its dispersion interactions. In the present study, the comparison of calculated (corrected) hydration free energies with experimental data (along with the consideration of ionic polarizabilities) is used to calibrate new sets of ion-solvent van der Waals (Lennard-Jones) interaction parameters for the alkali (Li(+), Na(+), K(+), Rb(+), Cs(+)) and halide (F(-), Cl(-), Br(-), I(-)) ions along with either the SPC or the SPC/E water models. The experimental dataset is defined by conventional single-ion hydration free energies [Tissandier et al., J. Phys. Chem. A 102, 7787 (1998); Fawcett, J. Phys. Chem. B 103, 11181] along with three plausible choices for the (experimentally elusive) value of the absolute (intrinsic) hydration free energy of the proton, namely, ΔG(hyd)(?)[H(+)] = -1100, -1075 or -1050 kJ mol(-1), resulting in three sets L, M, and H for the SPC water model and three sets L(E), M(E), and H(E) for the SPC/E water model (alternative sets can easily be interpolated to intermediate ΔG(hyd)(?)[H(+)] values). The residual sensitivity of the calculated (corrected) hydration free energies on the volume-pressure boundary conditions and on the effective ionic radius entering into the calculation of the correction terms is also evaluated and found to be very limited. Ultimately, it is expected that comparison with other experimental ionic properties (e.g., derivative single-ion solvation properties, as well as data concerning ionic crystals, melts, solutions at finite concentrations, or nonaqueous solutions) will permit to validate one specific set and thus, the associated ΔG(hyd)(?)[H(+)] value (atomistic consistency assumption). Preliminary results (first-peak positions in the ion-water radial distribution functions, partial molar volumes of ionic salts in water, and structural properties of ionic crystals) support a value of ΔG(hyd)(?)[H(+)] close to -1100 kJ·mol(-1).     

A molecular dynamics study of water nucleation using the TIP4P/2005 model

Extensive molecular dynamics simulations were conducted using the TIP4P/2005 water model of Abascal and Vega [J. Chem. Phys. 123, 234505 (2005)] to investigate its condensation from supersaturated vapor to liquid at 330 K. The mean first passage time method [J. Wedekind, R. Strey, and D. Reguera, J. Chem. Phys. 126, 134103 (2007); L. S. Bartell and D. T. Wu, 125, 194503 (2006)] was used to analyze the influence of finite size effects, thermostats, and charged species on the nucleation dynamics. We find that the Nose?-Hoover thermostat and the one proposed by Bussi et al. [J. Chem. Phys. 126, 014101 (2007)] give essentially the same averages. We identify the maximum thermostat coupling time to guarantee proper thermostating for these simulations. The presence of charged species has a dramatic impact on the dynamics, inducing a marked change towards a pure growth regime, which highlights the importance of ions in the formation of liquid droplets in the atmosphere. It was found a small but noticeable sign preference at intermediate cluster sizes (between 5 and 30 water molecules) corresponding mostly to the formation of the second solvation shell around the ion. The TIP4P/2005 water model predicts that anions induce faster formation of water clusters than cations of the same magnitude of charge.     

Comparison of different methods for calculating the paramagnetic relaxation enhancement of nuclear spins as a function of the magnetic field

The enhancement of the spin-lattice relaxation rate for nuclear spins in a ligand bound to a paramagnetic metal ion [known as the paramagnetic relaxation enhancement (PRE)] arises primarily through the dipole-dipole (DD) interaction between the nuclear spins and the electron spins. In solution, the DD interaction is modulated mostly by reorientation of the nuclear spin-electron spin axis and by electron spin relaxation. Calculations of the PRE are in general complicated, mainly because the electron spin interacts so strongly with the other degrees of freedom that its relaxation cannot be described by second-order perturbation theory or the Redfield theory. Three approaches to resolve this problem exist in the literature: The so-called slow-motion theory, originating from Swedish groups [Benetis et al., Mol. Phys. 48, 329 (1983); Kowalewski et al., Adv. Inorg. Chem. 57, (2005); Larsson et al., J. Chem. Phys. 101, 1116 (1994); T. Nilsson et al., J. Magn. Reson. 154, 269 (2002)] and two different methods based on simulations of the dynamics of electron spin in time domain, developed in Grenoble [Fries and Belorizky, J. Chem. Phys. 126, 204503 (2007); Rast et al., ibid. 115, 7554 (2001)] and Ann Arbor [Abernathy and Sharp, J. Chem. Phys. 106, 9032 (1997); Schaefle and Sharp, ibid. 121, 5387 (2004); Schaefle and Sharp, J. Magn. Reson. 176, 160 (2005)], respectively. In this paper, we report a numerical comparison of the three methods for a large variety of parameter sets, meant to correspond to large and small complexes of gadolinium(III) and of nickel(II). It is found that the agreement between the Swedish and the Grenoble approaches is very good for practically all parameter sets, while the predictions of the Ann Arbor model are similar in a number of the calculations but deviate significantly in others, reflecting in part differences in the treatment of electron spin relaxation. The origins of the discrepancies are discussed briefly.     

Analysis of experimental data for the nucleation rate of water droplets

A formula for the stationary nucleation rate J is proposed and used for analysis of experimental data for the dependence of J on the supersaturation ratio S in isothermal homogeneous nucleation of water droplets in vapors. It is found that the experimental data are described quite successfully by the proposed formula which is based on (i) the Gibbs presentation of the nucleation work in terms of overpressure, (ii) the Girshick-Chiu [J. Chem. Phys. 93, 1273 (1990); 94, 826 (1991)] self-consistency correction to the equilibrium cluster size distribution, and (iii) the Reguera-Rubi [J. Chem. Phys. 115, 7100 (2001)] kinetic accounting of the nucleus translational-rotational motion. The formula, like that of Wolk and Strey [J. Phys. Chem. B 105, 11683 (2001)], could be used as a semiempirical relation describing the J(S) dependence for nucleation in vapors of single-component droplets or crystals of substances with insufficiently well known equations of state.     

The I2 dissociation mechanisms in the chemical oxygen-iodine laser revisited

The recently suggested mechanism of I(2) dissociation in the chemical oxygen-iodine laser (COIL) [K. Waichman, B. D. Barmashenko, and S. Rosenwaks, J. Appl. Phys. 106, 063108 (2009); and J. Chem. Phys. 133, 084301 (2010)] was largely based on the suggestion of V. N. Azyazov, S. Yu. Pichugin, and M. C. Heaven [J. Chem. Phys. 130, 104306 (2009)] that the vibrational population of O(2)(a) produced in the chemical generator is high enough to play an essential role in the dissociation. The results of model calculations based on this mechanism agreed very well with measurements of the small signal gain g, I(2) dissociation fraction F, and temperature T in the COIL. This mechanism is here revisited, following the recent experiments of M. V. Zagidullin [Quantum Electron. 40, 794 (2010)] where the observed low population of O(2)(b, v = 1) led to the conclusion that the vibrational population of O(2)(a) at the outlet of the generator is close to thermal equilibrium value. This value corresponds to a very small probability, ～0.05, of O(2)(a) energy pooling to the states O(2)(X,a,b, v > 0). We show that the dissociation mechanism can reproduce the experimentally observed values of g, F, and T in the COIL only if most of the energy released in the processes of O(2)(a) energy pooling and O(2)(b) quenching by H(2)O ends up as vibrational energy of the products, O(2)(X,a,b), where the vibrational states v = 2 and 3 are significantly populated. We discuss possible reasons for the differences in the suggested vibrational population and explain how these differences can be reconciled.     

The role of the excited electronic states in the C+ + H2O reaction

The electronic excited states of the [COH2]+ system have been studied in order to establish their role in the dynamics of the C+ + H2O-->[COH]+ +H reaction, which is a prototypical ion-molecule reaction. The most relevant minima and saddle points of the lowest excited state have been determined and energy profiles for the lowest excited doublet and quartet electronic states have been computed along the fragmentation and isomerization coordinates. Also, nonadiabatic coupling strengths between the ground and the first excited state have been computed where they can be large. Our analysis suggests that the first excited state could play an important role in the generation of the formyl isomer, which has been detected in crossed beam experiments [D. M. Sonnenfroh et al., J. Chem. Phys. 83, 3985 (1985)], but could not be explained in quasiclassical trajectory computations [Y. Ishikawa et al., Chem. Phys. Lett. 370, 490 (2003); J. R. Flores, J. Chem. Phys. 125, 164309 (2006)].     

Supersonically cooled hydronium ions in a slit-jet discharge: high-resolution infrared spectroscopy and tunneling dynamics of HD2O+

Jet-cooled high-resolution infrared spectra of partially deuterated hydronium ion (HD2O+) in the O-H stretch region (nu3 band) are obtained for the first time, exploiting the high ion densities, long absorption path lengths, and concentration modulation capabilities of the slit-jet discharge spectrometer. Least-squares analysis with a Watson asymmetric top Hamiltonian yields rovibrational constants and provides high level tests of ab initio molecular structure predictions. Transitions out of both the lower (nu3(+)<--0(+)) and the upper (nu3(-)<--0(-)) tunneling levels, as well as transitions across the tunneling gap (nu3(-)<--0(+)) are observed. The nu3(-)<--0(+) transitions in HD2O+ acquire oscillator strength by loss of D(3h) symmetry, and permit both ground-state-[27.0318(72) cm(-1)] and excited-state-[17.7612(54) cm(-1)]-tunneling splittings to be determined to spectroscopic precision from a single rovibrational band. The splittings and band origins calculated with recent high level ab initio six-dimensional potential surface predictions for H3O+ and isotopomers [X. C. Huang, S. Carter, and J. M. Bowman, J. Chem. Phys. 118, 5431 (2003); T. Rajamaki, A. Miani, and L. Halonen, J. Chem. Phys. 118, 10929 (2003)] are in very good agreement with the current experimental results.