Submillimeterwave spectrum of CH2PH and equilibrium structures of CH2PH and CH2NH

Margulès, L.; Demaison, J.; Sreeja, P B; Guillemin, Jean‐Claude

doi:10.1016/j.jms.2006.05.008

Cited by 20 publications

(24 citation statements)

References 40 publications

(45 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Specifically, in addition to propyne, 12 nitrogen- and/or oxygen-bearing molecules have been added (HNO, NH 2 OH, CH 2 NH, CH 2 NOH, CO 2 , succinic anhydride, phenol, oxazole, isoxazole, glycidol, cyclopropenone, and glycine) and the number of sulfur compounds has been increased substantially with the inclusion of sulfur dioxide, dimethyl sulfide, dimethyl sulfoxide, sulfinylmethane, hydrogen disulfide, diallyl disulfide, and diphenyl disulfide, with the last three molecules involving a sulfur–sulfur bridge. Since phosphorus is a biologically relevant element not represented in the database, efforts have been made to overcome this limit, resulting in the inclusion of the PH 3 , CH 3 CP, CH 2 PH, and HPO molecules for which an accurate SE equilibrium geometry has been worked out in the literature. Furthermore, four boron-containing molecules have been introduced (BH 2 OH, BH(OH) 2 , BHFOH, and BH 3 NH 3 ), with the halogenated organics (1,1-ClFCCH 2 , OCHCl) as well as the inorganic compound HOF .…”

Section: Resultsmentioning

confidence: 99%

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Ceselin

Barone

Tasinato

2021

J. Chem. Theory Comput.

153

View full text Add to dashboard Cite

The determination of accurate equilibrium molecular structures plays a fundamental role for understanding many physical–chemical properties of molecules, ranging from the precise evaluation of the electronic structure to the analysis of the role played by dynamical and environmental effects in tuning their overall behavior. For small semi-rigid systems in the gas phase, state-of-the-art quantum chemical computations rival the most sophisticated experimental (from, for example, high-resolution spectroscopy) results. For larger molecules, more effective computational approaches must be devised. To this end, we have further enlarged the compilation of available semi-experimental (SE) equilibrium structures, now covering the most important fragments containing H, B, C, N, O, F, P, S, and Cl atoms collected in the new SE100 database. Next, comparison with geometries optimized by methods rooted in the density functional theory showed that the already remarkable results delivered by PW6B95 and, especially, rev-DSDPBEP86 functionals can be further improved by a linear regression (LR) approach. Use of template fragments (taken from the SE100 library) together with LR estimates for the missing interfragment parameters paves the route toward accurate structures of large molecules, as witnessed by the very small deviations between computed and experimental rotational constants. The whole approach has been implemented in a user-friendly tool, termed nano-LEGO, and applied to a number of demanding case studies.

show abstract

Section: Resultsmentioning

confidence: 99%

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Ceselin

Barone

Tasinato

2021

J. Chem. Theory Comput.

153

View full text Add to dashboard Cite

show abstract

“…A reinvestigation of the rotational spectrum of CH 2 PH and large basis set CCSD(T) calculations of its structure have been reported, 50 thus providing an improved estimate of the equilibrium structure of CH 2 PH. 8: CCSD(T)/6-311G** C)P and P-X Harmonic Stretching Frequencies (cm -1 ) and Infrared Intensities (km mol -1 ) for CH 2 dPX (X ) H, F, Cl, and Br) CdP P -X …”

Section: Discussionmentioning

confidence: 99%

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))

Watts

Huang

2009

J. Phys. Chem. A

View full text Add to dashboard Cite

Ab initio theoretical calculations have been used to study the influence of phosphorus substituents, Y, on the tautomerism between the vinylphosphine XP(H)C(CH(3))=CH(2) and the phosphaalkene XP=C(CH(3))(2) (X = H, F, Cl, Br, OH, and Ar(F); Ar(F) = 2,6-(CF(3))(2)C(6)H(3)) and on the acidity of the aforementioned vinylphosphine. The stabilization of the phosphaalkene and the increased acidity of the vinylphosphine by Ar(F) are possible factors in the successful synthesis of certain isolable phosphaalkenes. In this work, the properties of Ar(F) are assessed theoretically. Density functional theory using the B3LYP functional has been used for all substituents. In addition, coupled-cluster singles and doubles with noniterative triples (CCSD(T)) has been used for X = H, F, Cl, Br, and OH. The phosphaalkene is favored over the vinylphosphine for all substituents, with F having the strongest stabilizing effect. Cl, Br, and OH have stronger stabilizing effects than Ar(F). In contrast, the most acidic vinylphosphine is that with Ar(F). To aid in the interpretation and analysis of future experimental work, CCSD(T) calculations were used to provide structures and vibrational frequencies for the series XP=C(CH(3))(2) (X = H, F, Cl, Br). The influence of the substituent on geometries and C=P and X-P stretching frequencies was examined, and comparisons were made with the CH(2)=PX series.

show abstract

“…When the number of data is large enough to do such a check, it indeed appears that the residuals are far from random. For instance, in the case of CH 2 @PH [32], most of the residuals for the A-constants are negative (the only positive ones correspond to the CD 2 @PH/D species) with a mean equal to À2.14 MHz and a median equal to À1. 89 MHz, values which are larger than the estimated accuracy of the ground state A-constants which is about 5 kHz.…”

Section: Moleculementioning

confidence: 99%

Accuracy of the rotational constants

Vogt

Demaison

2011

Journal of Molecular Structure

View full text Add to dashboard Cite

Submillimeterwave spectrum of CH2PH and equilibrium structures of CH2PH and CH2NH

Cited by 20 publications

References 40 publications

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))

Accuracy of the rotational constants

Contact Info

Product

Resources

About

Submillimeterwave spectrum of CH2PH and equilibrium structures of CH2PH and CH2NH

Cited by 20 publications

References 40 publications

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Accurate Biomolecular Structures by the Nano-LEGO Approach: Pick the Bricks and Build Your Geometry

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH3)2(X = H, F, Cl, Br, OH, ArF(ArF= 2,6-(CF3)2C6H3))

Accuracy of the rotational constants

Contact Info

Product

Resources

About

Theoretical Study of the Tautomerism, Structures, and Vibrational Frequencies of the Phosphaalkenes XP═C(CH₃)₂(X = H, F, Cl, Br, OH, Ar_F(Ar_F= 2,6-(CF₃)₂C₆H₃))