Accurate heats of atomization and accurate bond lengths.: II. Polyenes and polyphenyls

1968 ◽  
Vol 46 (12) ◽  
pp. 2041-2051 ◽  
Author(s):  
Donald H. Lo ◽  
M. A. Whitehead
Keyword(s):  
Steric Hindrance ◽  
Bond Order ◽  
Minimum Energy ◽  
Stabilization Energy ◽  
Direct Measure ◽  
Bond Lengths ◽  
Molecular Stability ◽  
Linear Polyenes ◽  
Substituted Polyenes ◽  
Good Agreement

Accurate heats of atomization and bond lengths are calculated for several polyenes and polyphenyls, using the s.c.f.–l.c.a.o.–m.o. method described in Part I (1). Localization of π and σ bonds is found in the linear polyenes and in the diphenyl-substituted polyenes. The estimated stabilization energy per CC bond (SECC) gives a direct measure of the π electron conjugation and σ bond compression. Conjugation stabilization and steric hindrance are analyzed in 1,3-butadiene and biphenyl; the predicted geometries are in good agreement with experimental results. The minimum energy for any planar structure is found to be associated with the s.c.f. calculated bond lengths. The validity of pi bond order as a measure of molecular stability in the polyphenyls is discussed.

N.M.R.-Studies of Bond Order in Azulene, Biphenylene and 1,6-Methano[10]annulene

1990 ◽  
Vol 43 (9) ◽  
pp. 1541 ◽  
Author(s):  
MJ Collins ◽  
S Sternhell ◽  
CW Tansey
Keyword(s):  
Experimental Data ◽  
Ground State ◽  
Bond Order ◽  
Membered Ring ◽  
Coupling Constants ◽  
Bond Orders ◽  
Bond Lengths ◽  
Theoretical Predictions ◽  
Electron Distributions ◽  
Good Agreement

The 4J(H-C-C-Me) coupling constants of methyl-substituted derivatives, probes of bond order, have been used to examine the ground-state π- electron distributions in azulene (1), biphenylene (2) and 1,6- methano [10] annulene (3). The experimental data obtained are in good agreement with theoretical predictions for biphenylene (2) and provide some evidence for π-electron disproportionation towards the five-membered ring in azulene (1). The bond orders in 1,6-methano [10] annulene (3) obtained in this work are at variance with those predicted on the grounds of bond lengths.

scholarly journals Bi-Dimensional Deflection Estimation by Embedded Fiber Bragg Gratings Sensors

Proceedings ◽  
2019 ◽  
Vol 15 (1) ◽  
pp. 3
Author(s):  
Palma ◽  
Palumbo ◽  
Pietra ◽  
Canale ◽  
Alviggi ◽  
...  
Keyword(s):  
Real Time ◽  
Fiber Bragg Gratings ◽  
Beam Theory ◽  
Bragg Gratings ◽  
Strain Sensors ◽  
Structural Monitoring ◽  
Direct Measure ◽  
Large Structure ◽  
Good Agreement ◽  
Classical Beam Theory

In this work, we present and discuss on the deflection estimation of a bi-dimensional panel by using Fiber Bragg Gratings (FBGs) as strain sensors embedded in the structure and a method based on the classical beam theory. The existing difficulties in the direct measure of the deflection are overcome thanks to the proposed technique and a real-time indirect structural monitoring is possible both on small and large structure. In many tests the estimated deflection with the proposed method has been compared with direct deflection measurements obtained with a mechanical comparator showing good agreement. A resolution of few tens of microns over a surface of the order of 1 m2 has been reached.

Growth and Atomistic Structure Study of Disordered SiGe Mixed Semiconductors

2007 ◽  
Vol 539-543 ◽  
pp. 2043-2047 ◽  
Author(s):  
Ichiro Yonenaga ◽  
Masaki Sakurai ◽  
Marcel H.F. Sluiter
Keyword(s):  
Structure Study ◽  
Suitable Model ◽  
Bond Lengths ◽  
Random Mixture ◽  
Mixed Material ◽  
X Ray Absorption ◽  
Ab Inito ◽  
Structure Calculations ◽  
Atomistic Structure ◽  
Good Agreement

The atomistic structure of Czochralski-grown SixGe1-x binary mixed semiconductor was studied experimentally and theoretically. By extended X-ray absorption fine structure (XAFS) studies it was found that bulk SiGe semiconductor is a random mixture and that the Ge-Ge, Ge-Si and Si-Si bond lengths maintain distinctly different lengths and vary in a linear fashion against the alloy composition across the whole composition range 0 < x < 1, in good agreement with expectations derived from the ab-inito electronic structure calculations. The result indicates that SiGe is a suitable model for a disorder mixed material and that the bond lengths and bond angles are distorted with the composition.

scholarly journals Which Is the Motion State of a Droplet on an Inclined Hydrophilic Rough Surface in Gravity: Pinned or Sliding?

2021 ◽  
Vol 11 (9) ◽  
pp. 3734
Author(s):  
Jian Dong ◽  
Youhai Guo ◽  
Long Jiao ◽  
Chao Si ◽  
Yinbo Bian ◽  
...  
Keyword(s):  
Rough Surface ◽  
Contact Angle Hysteresis ◽  
Minimum Energy ◽  
Contact Angles ◽  
Microfluidic Chips ◽  
Motion State ◽  
Receding Contact ◽  
Novel Design ◽  
Minimum Energy Dissipation ◽  
Good Agreement

The motion state of a droplet on an inclined, hydrophilic rough surface in gravity, pinned or sliding, is governed by the balance between the driving and the pinned forces. It can be judged by the droplet’s shape on the inclined hydrophilic rough surface and the droplet’s contact angle hysteresis. In this paper, we used the minimum energy theory, the minimum energy dissipation theory, and the nonlinear numerical optimization algorithm to establish Models 1–3 to calculate out the advancing/receding contact angles (θa/θr), the initial front/rear contact angles (θ1−0/θ2−0) and the dynamic front/rear contact angles (θ1−*/θ2−*) for a droplet on a rough surface. Also, we predicted the motion state of the droplet on an inclined hydrophilic rough surface in gravity by comparing θ1−0(θ2−0) and θ1−*(θ2−*) with θa(θr). Experiments were done to verify the predictions. They showed that the predictions were in good agreement with the experimental results. These models are promising as novel design approaches of hydrophilic functional rough surfaces, which are frequently applied to manipulate droplets in microfluidic chips.

scholarly journals Comparison of molecular structures of cis-bis[8-(dimethylphosphanyl)quinoline]nickel(II) and -platinum(II) complex cations

2020 ◽  
Vol 76 (12) ◽  
pp. 1813-1817
Author(s):  
Masatoshi Mori ◽  
Takayoshi Suzuki
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Steric Hindrance ◽  
Molecular Structures ◽  
Coordination Geometry ◽  
Donor Group ◽  
Bending Deformation ◽  
Bond Lengths ◽  
Square Planar ◽  
Chelate Ligands

The crystal structures of the complexes (SP-4-2)-cis-bis[8-(dimethylphosphanyl)quinoline-κ2 N,P]nickel(II) bis(perchlorate) nitromethane monosolvate, [Ni(C11H12NP)2](ClO4)2·CH3NO2 (1), and (SP-4-2)-cis-bis[8-(dimethylphosphanyl)quinoline-κ2 N,P]platinum(II) bis(tetrafluoroborate) acetonitrile monosolvate, [Pt(C11H12NP)2](BF4)2·C2H3N (2), are reported. In both complex cations, two phosphanylquinolines act as bidentate P,N-donating chelate ligands and form the mutually cis configuration in the square-planar coordination geometry. The strong trans influence of the dimethylphosphanyl donor group is confirmed by the Ni—N bond lengths in 1, 1.970 (2) and 1.982 (2) Å and, the Pt—N bond lengths of 2, 2.123 (4) and 2.132 (4) Å, which are relatively long as compared to those in the analogous 8-(diphenylphosphanyl)quinoline complexes. Mutually cis-positioned quinoline donor groups would give a severe steric hindrance between their ortho-H atoms. In order to reduce such a steric congestion, the NiII complex in 1 shows a tetrahedral distortion of the coordination geometry, as parameterized by τ4 = 0.199 (1)°, while the PtII complex in 2 exhibits a typical square-planar coordination geometry [τ4 = 0.014 (1)°] with a large bending deformation of the ideally planar Me2Pqn chelate planes. In the crystal structure of 2, three F atoms of one of the BF4 − anions are disordered over two sets of positions with refined occupancies of 0.573 (10) and 0.427 (10).

Bond order-bond length relationships in conjugated hydrocarbons - the microwave spectrum and structure of 3,4-dimethylenecyclobutene

1983 ◽  
Vol 36 (4) ◽  
pp. 639 ◽  
Author(s):  
RD Brown ◽  
PD Godfry ◽  
BT Hart ◽  
AL Ottrey ◽  
M Onda ◽  
...  
Keyword(s):  
Dipole Moment ◽  
Ab Initio ◽  
Bond Length ◽  
Bond Order ◽  
Microwave Spectrum ◽  
Basis Set ◽  
Molecular Orbital Calculations ◽  
Bond Orders ◽  
Bond Lengths ◽  
Typical Error

The microwave spectrum of the benzene isomer 3,4-dimethylenecyclobutene including spectra of all possible single 13C-substituted and sufficient singly and doubly D-substituted species to give a complete r5 geometry, have been measured and analysed. An estimate of the re geometry has also been derived. The additional precise CC bond lengths obtained for an unsubstituted, conjugated hydrocarbon enable us to examine bond order-bond length relationships more thoroughly than has previously been possible. The CC bond lengths exhibit a noticeably better correlation with SCFMO bond orders than with simple H�ckel bond orders. Further confirmatory measurements of the dipole moment of dimethylenecyclobutene have been made. Ab initio molecular orbital calculations using a 6-31G basis set give an optimized geometry with CC bond lengths within 2 pm of the r5 values. The computed dipole moment agrees almost exactly with experiment but a corresponding calculation on fulvene is discrepant with experiment by 0.16 D, which is probably a more typical error.

Bond Lengths in Conjugated Molecules: The Present Position

1951 ◽  
Vol 207 (1088) ◽  
pp. 91-100 ◽  
Keyword(s):  
Bond Order ◽  
Empirical Relation ◽  
Simple Theory ◽  
Reliable Estimate ◽  
Present Position ◽  
Conjugated Molecules ◽  
X Ray ◽  
Bond Lengths ◽  
Hydrocarbon Molecules ◽  
Semi Empirical

A survey is given of the present methods for calculating bond lengths in conjugated molecules. Except in simple cases this has to be achieved by combining a calculated bond order with a semi-empirical relation between order and length. There are several definitions of bond order in current use, some of which can be shown to be less valuable than others. Recent accurate X -ray analysis has shown convincingly that the concept of bond order is a valid one, though there are limits to the degree of accuracy that may be claimed. Several possible improvements upon the simple theory are mentioned, most of which indicate alterations in bond lengths calculated from the simple theory, of the order of 0.005 Å. It is concluded that for condensed hydrocarbon molecules, the lengths of individual bonds may be predicted to within about 0.015 Å. For heteromolecules there are still too many additional factors for any reliable estimate to be possible.

O-Benzoyl side-chain conformations in 2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl-(1→4)-1,2,6-tri-O-benzoyl-β-D-glucopyranose (ethyl acetate solvate) and 1,2,4,6-tetra-O-benzoyl-β-D-glucopyranose (acetone solvate)

2019 ◽  
Vol 75 (2) ◽  
pp. 161-167 ◽  
Author(s):  
Toby Turney ◽  
Qingfeng Pan ◽  
Wenhui Zhang ◽  
Allen G. Oliver ◽  
Anthony S. Serianni
Keyword(s):  
Ethyl Acetate ◽  
Bond Angle ◽  
Solution Nmr ◽  
Side Chain ◽  
Nmr Studies ◽  
Torsion Angles ◽  
Bond Lengths ◽  
Side Chain Conformation ◽  
Chain Conformations ◽  
Good Agreement

The crystal structures of 2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl-(1→4)-1,2,6-tri-O-benzoyl-β-D-glucopyranose ethyl acetate hemisolvate, C61H50O18·0.5C4H8O2, and 1,2,4,6-tetra-O-benzoyl-β-D-glucopyranose acetone monosolvate, C34H28O10·C3H6O, were determined and compared to those of methyl β-D-galactopyranosyl-(1→4)-β-D-glucopyranoside (methyl β-lactoside) and methyl β-D-glucopyranoside hemihydrate, C7H14O6·0.5H2O, to evaluate the effects of O-benzoylation on bond lengths, bond angles and torsion angles. In general, O-benzoylation exerts little effect on exo- and endocyclic C—C and endocyclic C—O bond lengths, but exocyclic C—O bonds involved in O-benzoylation are lengthened by 0.02–0.04 Å depending on the site of substitution. The conformation of the O-benzoyl side-chains is highly conserved, with the carbonyl O atom either eclipsing the H atom attached to a 2°-alcoholic C atom or bisecting the H—C—H bond angle of an 1°-alcoholic C atom. Of the three bonds that determine the side-chain geometry, the C—O bond involving the alcoholic C atom exhibits greater rotational variability than the remaining C—O and C—C bonds involving the carbonyl C atom. These findings are in good agreement with recent solution NMR studies of the O-acetyl side-chain conformation in saccharides.

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