Quantum Structure of the Intermolecular Proton Bond

Roscioli, Joseph R.; McCunn, Laura R.; Johnson, Mark A.

doi:10.1126/science.1138962

Cited by 253 publications

(405 citation statements)

References 26 publications

(48 reference statements)

Supporting

Mentioning

369

Contrasting

Unclassified

Order By: Relevance

“…For proton-bound heterodimers, one can estimate ν x p from the difference in proton affinity of the two groups. 53 Here, we propose that for proton-bound homodimers one may use the dependence of ν x p on the distance r of the (heavy) atoms sharing the proton, i.e., r OO in the present case, as a criterion for the assignment of ν x p in the equally shared proton regime. 59 respectively, while the predicted values for r (for the equally shared proton configuration) are 2.75 Å, 57 2.51 Å, 58 and 2.44 Å (present work, C 2h geometry), and 2.40 Å, 60 respectively.…”

Section: Discussionmentioning

confidence: 99%

Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO₃^–(HNO₃)_m(H₂O)_n

et al. 2014

View full text Add to dashboard Cite

Infrared multiple photon dissociation (IRMPD) spectra of NO 3 − (HNO 3 ) m (H 2 O) n (H 2 ) z with m = 1−3, up to n = 8 and z ≥ 1, are measured in the fingerprint region (550−1880 cm −1 ), directly probing the NO-stretching modes, as well as bending and other lower frequency modes. The assignment of the spectra is aided by electronic structure calculations. The IRMPD spectrum of the m = 1, n = 0 cluster is distinctly different from all the other measured spectra as a result of strong hydrogen bonding, leading to an equally shared proton in between two nitrate moieties (O 2 NO − ···H + ··· ONO 2 − ). It exhibits a strong absorption at 877 cm −1 and lacks the characteristic NO 2 -antisymmetric stretching/NOH-bending mode absorption close to 1650 cm −1 . Addition of at least one more nitric acid molecule or two more water molecules weakens the hydrogen bond network, breaking the symmetry of this arrangement and leading to localization of the proton near one of the nitrate cores, effectively forming HNO 3 hydrogen-bonded to NO 3 − . Not all IR active modes are observed in the IRMPD spectra of the bare nitrate−nitric acid clusters. Addition of a water or a hydrogen molecule lowers the dissociation limit of the complexes and relaxes (H 2 O) or lifts (H 2 ) this IRMPD transparency.

show abstract

Section: Discussionmentioning

confidence: 99%

Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO₃^–(HNO₃)_m(H₂O)_n

et al. 2014

View full text Add to dashboard Cite

show abstract

“…The former is conspicuously absent in the experimental spectrum while the observed bands near 1400 cm -1 appear significantly weaker than the calculated intensity of the H-bonded mode. The absence of these bands is readily explained by the anharmonicity associated with strongly shared protons in a variety of contexts [51][52][53][54][55], and is explicitly addressed in the context of all four systems in the Anharmonicity of the Intramolecular H-bond section.…”

Section: Glyglyhmentioning

confidence: 99%

“…+ B] systems [51], where larger differences in proton affinities between donor and acceptor molecules gave rise to higher frequency bands.…”

Section: Anharmonicity Of the Intramolecular H-bondmentioning

confidence: 99%

Characterizing the Intramolecular H-bond and Secondary Structure in Methylated GlyGlyH⁺ with H₂ Predissociation Spectroscopy

Leavitt

Wolk

Kamrath

et al. 2011

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

We report vibrational predissociation spectra of the four protonated dipeptides derived from glycine and sarcosine, GlyGlyH•(H 2 ) 2 , and SarSarH + •(D 2 ) 2 , generated in a cryogenic ion trap. Sharp bands were recovered by monitoring photoevaporation of the weakly bound H 2 (D 2 ) molecules in a linear action regime throughout the 700-4200 cm -1 range using a table-top laser system. The spectral patterns were analyzed in the context of the low energy structures obtained from electronic structure calculations. These results indicate that all four species are protonated on the N-terminus, and feature an intramolecular H-bond involving the amino group. The large blue-shift in the H-bonded N-H fundamental upon incorporation of a methyl group at the N-terminus indicates that this modification significantly lowers the strength of the intramolecular H-bond. Methylation at the amide nitrogen, on the other hand, induces a significant rotation (~110 o ) about the peptide backbone.

show abstract

“…It is a well-known feature of the IRMPD spectra of noncovalent adducts that contain NH and OH hydrogen-bond donors that their stretching vibrations can be more or less red-shifted and broadened, depending upon their relevant dissociation threshold. [34,46,47,[50][51][52][53][54][55][56] The broad resonances at 3100-3300 cm À1 …”

Section: Discussionmentioning

confidence: 99%

Chirality Effects on the IRMPD Spectra of Basket Resorcinarene/Nucleoside Complexes

Filippi

Fraschetti

Piccirillo

et al. 2012

Chemistry A European J

View full text Add to dashboard Cite

The IRMPD spectra of the ESI‐formed proton‐bound complexes of the R,R,R,R‐ and S,S,S,S‐enantiomers of a bis(diamido)‐bridged basket resorcin[4]arene (R and S) with cytosine (1), cytidine (2), and cytarabine (3) were measured in the region 2800–3600 cm−1. Comparison of the IRMPD spectra with the corresponding ONIOM (B3LYP/6‐31(d):UFF)‐calculated absorption frequencies allowed the assessment of the vibrational modes that are responsible for the observed spectroscopic features. All of the complexes investigated, apart from [R⋅H⋅3]+, showed similar IRMPD spectra, which points to similar structural and conformational landscapes. Their IRMPD spectra agree with the formation of several isomeric structures in the ESI source, wherein the N(3)‐protonated guest establishes noncovalent interactions with the host amidocarbonyl groups that are either oriented inside the host cavity or outside it between one of the bridged side‐chains and the upper aromatic nucleus. The IRMPD spectrum of the [R⋅H⋅3]+ complex was clearly different from the others. This difference is attributed to the effect of intramolecular hydrogen‐bonding interactions between the C(2′)OH group and the aglycone oxygen atom of the nucleosidic guest upon repulsive interactions between the same oxygen atom and the aromatic rings of the host.

show abstract

Quantum Structure of the Intermolecular Proton Bond

Cited by 253 publications

References 26 publications

Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO₃^–(HNO₃)_m(H₂O)_n

Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO₃^–(HNO₃)_m(H₂O)_n

Characterizing the Intramolecular H-bond and Secondary Structure in Methylated GlyGlyH⁺ with H₂ Predissociation Spectroscopy

Chirality Effects on the IRMPD Spectra of Basket Resorcinarene/Nucleoside Complexes

Contact Info

Product

Resources

About

Quantum Structure of the Intermolecular Proton Bond

Cited by 253 publications

References 26 publications

Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO3–(HNO3)m(H2O)n

Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO3–(HNO3)m(H2O)n

Characterizing the Intramolecular H-bond and Secondary Structure in Methylated GlyGlyH+ with H2 Predissociation Spectroscopy

Chirality Effects on the IRMPD Spectra of Basket Resorcinarene/Nucleoside Complexes

Contact Info

Product

Resources

About

Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO₃^–(HNO₃)_m(H₂O)_n

Infrared Photodissociation Spectroscopy of Microhydrated Nitrate–Nitric Acid Clusters NO₃^–(HNO₃)_m(H₂O)_n

Characterizing the Intramolecular H-bond and Secondary Structure in Methylated GlyGlyH⁺ with H₂ Predissociation Spectroscopy