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The appearance of multiple bands in the N–H stretching region of the infrared spectra of the neutral methylamine dimer and trimer is a sign of NH bend–stretch anharmonic coupling. Ab initio anharmonic calculations were carried out in a step-wise manner to reveal the origin of various bands observed in the spectrum of the methylamine dimer. A seven-dimensional potential energy surface involving symmetric and asymmetric stretching and bending vibrations of both the hydrogen bond donor and the acceptor along intermolecular-translational modes was constructed using the discrete variable representation approach. The resulting spectrum of the dimer shows five bands that can be attributed to the symmetric stretching ( ν sym D ), asymmetric stretchin ( ν asym D ), and bending overtone (2 ν bend D ) of the donor moiety. These appear along with the combination band arising out of bending vibrations of the donor and acceptor ( ν bend D + ν bend A ) and with the combination of the intermolecular translational mode over the donor bending overtone ( ν trans + 2 ν bend D ). The spectrum of the trimer essentially consists of all the features seen in the dimer with marginal changes in band positions. The analysis of the experimental spectra based on the two-state deperturbation model and ab initio anharmonic calculations yield a matrix element of about 40 cm−1 for the N–H bend–stretch Fermi resonance coupling. In general, the IR spectra of the hydrogen-bonded amino group depict three sets of bands that arise due to bend–stretch Fermi resonance coupling. [ABSTRACT FROM AUTHOR]

The infrared spectrum of proton-bound rare gas dimers has been extensively studied via matrix isolation spectroscopy. However, little attention has been paid on their spectrum in the gas phase. Most of the Rg2H+ has not been detected outside the matrix environment. Recently, ArnH+ (n = 3-7) has been first detected in the gas-phase [D. C. McDonald et al., J. Chem. Phys. 145, 231101 (2016)]. In that work, anharmonic theory can reproduce the observed vibrational structure. In this paper, we extend the existing theory to examine the vibrational signatures of Rg2H+, Rg = {Ne, Ar, Kr, and Xe}. The successive binding of Rg to H+ was investigated through the calculation of stepwise formation energies. It was found that this binding is anti-cooperative. High-level full-dimensional potential energy surfaces at the CCSD(T)/aug-cc-pVQZ//MP2/aug-cc-pVQZ were constructed and used in the anharmonic calculation via discrete variable representation. We found that the potential coupling between the symmetric and asymmetric Rg-H+ stretch (ν1 and ν3 respectively) causes a series of bright n1ν1 + ν3 progressions. From Ne2H+ to Xe2H+, an enhancement of intensities for these bands was observed. [ABSTRACT FROM AUTHOR]

Infrared-vacuum ultraviolet (IR-VUV) spectra of neutral dimethylamine clusters, (DMA)n (n = 2–5), were measured in the spectral range of 2600–3700 cm−1. The experimental IR-VUV spectra show NH stretch modes gradually redshift to 3200-3250 cm−1 with the increase in the cluster size and complex Fermi Resonance (FR) pattern of the CH3 group in the 2800–3000 cm−1 region. Ab initio anharmonic vibrational calculations were performed on low-energy conformers of (DMA)2 and (DMA)3 to examine vibrational coupling among CH/NH and to understand the Fermi resonance pattern in the observed spectra features. We found that the redshift of NH stretching mode with the size of DMA cluster is moderate, and the overtone of NH bending modes is expected to overlap in frequency with the CH stretching fundamental modes. The FR in CH3 groups is originated from the strong coupling between CH stretching fundamental and bending overtone within a CH3 group. Well-resolved experimental spectra also enable us to compare the performance of ab initio anharmonic algorithms at different levels. [ABSTRACT FROM AUTHOR]

Infrared spectra for a series of asymmetric proton‐bound dimers with protonated trimethylamine (TMA‐H+) as the proton donor were recorded and analyzed. The frequency of the N–H+ stretching mode is expected to red shift as the proton affinity of proton acceptors increases. The observed band, however, shows a peculiar splitting of approximately 300 cm−1 with the intensity shifting pattern resembling a two‐level system. Theoretical investigation reveals that the observed band splitting and its extraordinarily large gap of around 300 cm−1 is a result of strong coupling between the fundamental of the proton stretching mode and overtone states of the two proton bending modes, that is commonly known as Fermi resonance (FR). We also provide a general theoretical model to link the strong FR coupling to the quasi‐two‐level system. Since the model does not depend on the molecular specification of TMA‐H+, the strong coupling we observed is an intrinsic property associated with proton motions. [ABSTRACT FROM AUTHOR]