A theoretical forecast of the hydrogen bond changes in the electronic excited state for BN and its derivatives

Open Physics ◽  
2012 ◽  
Vol 10 (1) ◽  
Author(s):  
Dandan Wang ◽  
Ce Hao ◽  
Se Wang ◽  
Hong Dong ◽  
Jieshan Qiu
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Excited States ◽  
Electronic Spectra ◽  
Intermolecular Hydrogen Bond ◽  
Excitation Energies ◽  
Electronically Excited States ◽  
Electronically Excited ◽  
Accurate Forecast ◽  
Hydrogen Bonding Dynamics

AbstractThe relationship between electronic spectral shifts and hydrogen-bonding dynamics in electronically excited states of the hydrogen-bonded complex is put forward. Hydrogen bond strengthening will induce a redshift of the corresponding electronic spectra, while hydrogen bond weakening will cause a blueshift. Time-dependent density function theory (TDDFT) was used to study the excitation energies in both singlet and triplet electronically excited states of Benzonitrile (BN), 4-aminobenzonitrile (ABN), and 4-dimethylaminobenzonitrile (DMABN) in methanol solvents. Only the intermolecular hydrogen bond C≡N...H-O was involved in our system. A fairly accurate forecast of the hydrogen bond changes in lowlying electronically excited states were presented in light of a very thorough consideration of their related electronic spectra. The deduction we used to depict the trend of the hydrogen bond changes in excited states could help others understand hydrogen-bonding dynamics more effectively.

Excited-state hydrogen bonding dynamics of methyl isocyanide in methanol solvent: A DFT/TDDFT study

Open Physics ◽  
2011 ◽  
Vol 9 (3) ◽  
Author(s):  
Hongfei Wang ◽  
Meishan Wang ◽  
Mingliang Xin ◽  
Enfu Liu ◽  
Chuanlu Yang
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Excited State ◽  
Excited States ◽  
Intermolecular Hydrogen Bond ◽  
Hydrogen Bond Acceptor ◽  
Electronically Excited States ◽  
Electronically Excited ◽  
Hydrogen Bonding Dynamics ◽  
Hydrogen Bonded

AbstractThe time-dependent density functional theory (TDDFT) method was performed to investigate the hydrogenbonding dynamics of methyl cyanide (MeNC) as hydrogen bond acceptor in hydrogen donating methanol (MeOH) solvent. The ground-state geometry optimizations and electronic transition energies and corresponding oscillation strengths of the low-lying electronically excited states for the isolated MeNC and MeOH monomers, the hydrogen-bonded MeNC-MeOH dimer and MeNC-2MeOH trimer are calculated by the DFT and TDDFT methods, respectively. An intermolecular hydrogen bond N≡C…H-O is formed between MeNC and methanol molecule. According to Zhao’s rule on the excited-state hydrogen bonding dynamics, we find the intermolecular hydrogen bonds N≡C…H-O are strengthened in electronically excited states of the hydrogen-bonded MeNC-MeOH dimer and MeNC-2MeOH trimer, with the excitation energy of a related excited state being lowered and electronic spectral redshifts being induced. Furthermore, the hydrogen bond strengthening in the electronically excited state plays an important role on the photophysics and photochemistry of MeNC in solutions

scholarly journals Hydrogen-bonding study of photoexcited 4-nitro-1,8-naphthalimide in hydrogen-donating solvents

Open Physics ◽  
2016 ◽  
Vol 14 (1) ◽  
pp. 621-627
Author(s):  
Jianfang Cao ◽  
Hongmei Wu ◽  
Yue Zheng ◽  
Fangyuan Nie ◽  
Ming Li ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Hydrogen Bond ◽  
Excited States ◽  
Density Functional ◽  
Intermolecular Hydrogen Bond ◽  
Excitation Energies ◽  
Hydrogen Bond Acceptor ◽  
Functional Theory ◽  
Electronically Excited ◽  
Hydrogen Bonded

AbstractThe solute–solvent interactions of 4-nitro-1,8-naphthalimide (4NNI) as a hydrogen bond acceptor in hydrogen donating methanol (MeOH) solvent in electronic excited states were investigated by means of the time-dependent density functional theory(TDDFT). We calculated the S0 state geometry optimizations, electronic transition energies and corresponding oscillation strengths of the low-lying electronically excited states for the isolated 4NNi and hydrogen-bonded 4NNi-(MeOH)1,4 complexes using the density functional theory (DFT) and TDDFT methods. The electronic excitation energies of the hydrogen-bonded complexes are correspondingly decreased compared to that of the isolated 4NNi, which revealed that the intermolecular hydrogen bond C=O···H–O and N=O···H–O in the hydrogen-bonded 4NNi-(MeOH)1,4 are strengthened in the electronically excited state. The calculated results are consistent with the mechanism that hydrogen bond strengthening will induce a redshift of the corresponding electronic spectra, while hydrogen bond weakening will cause a blueshift. Furthermore, we believe that the deduction we used to depict the trend of the hydrogen bond changes in excited states exists in many other fuorescent dyes in solution.

STRUCTURAL AND SOLVENT EFFECTS ON THE n → π*(′U ← ′A) TRANSITIONS IN ALIPHATIC CARBONYL DERIVATIVES: EVIDENCE FOR HYPERCONJUGATION IN THE ELECTRONICALLY EXCITED STATES OF MOLECULES

1960 ◽  
Vol 38 (12) ◽  
pp. 2508-2513 ◽  
Author(s):  
C. N. R. Rao ◽  
G. K. Goldman ◽  
A. Balasubramanian
Keyword(s):  
Hydrogen Bonding ◽  
Carbonyl Group ◽  
Excited States ◽  
Solvent Effects ◽  
Electronically Excited States ◽  
Carbonyl Derivatives ◽  
Alkyl Groups ◽  
Electronically Excited

The n → π* transition of the carbonyl group has been studied in solvents of varying degree of polarity and hydrogen-bonding ability, in a number of aliphatic carbonyl derivatives. Evidence for hyperconjugation of the alkyl groups in the electronically excited states of molecules has been presented.

The structure and vertical excitation energies of the chlorothioformyl radical, ClCS: implications for the photofragmentation of thiophosgene

1993 ◽  
Vol 71 (1) ◽  
pp. 112-117 ◽  
Author(s):  
M. Hachey ◽  
F. Grein ◽  
R. P. Steer
Keyword(s):  
Energy Level ◽  
Ab Initio ◽  
Excited States ◽  
Ground State ◽  
Excited Electronic State ◽  
Excitation Energies ◽  
Electronically Excited States ◽  
Vertical Excitation ◽  
Electronically Excited ◽  
Vertical Excitation Energies

Ab initio CI studies have been performed to determine the geometry of the ground and first electronically excited states of the chlorothioformyl radical, ClCS, and the vertical excitation energies of its ten lowest doublet states and two lowest quartet states. The results are used to construct a more complete energy level correlation diagram for the photofragmentation of Cl2CS. The lowest excited electronic state of ClCS lies only 0.79 eV (adiabatic) above the ground state. Its discovery indicates that the results of previous photofragmentation experiments may need to be reinterpreted.

A theoretical study of hydration effects on structural stability and hydrogen-bonding dynamics of 2′-deoxyguanosine 5′-monophosphate with different negative charges

2013 ◽  
Vol 91 (2) ◽  
pp. 169-175
Author(s):  
Weiping Zhang ◽  
Xiaoyu Zhang
Keyword(s):  
Density Functional Theory ◽  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Density Functional ◽  
Negative Charge ◽  
Solvation Shell ◽  
Excitation Energies ◽  
Functional Theory ◽  
Hydrogen Bonding Dynamics

The effects of hydration on the ground-state structural stability and excited-state hydrogen-bonding dynamics of 2′-deoxyguanosine 5′-monophosphate (dGMP) carrying different negative charges were investigated with B3LYP/6–31+G(d,p) using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, respectively. Particularly, we not only considered the solvent effects by the polarizible continuum model (PCM), but also the first solvation shell was included explicitly. We demonstrated that the intramolecular hydrogen bond O2–H1···O3 will be weakened with the strengthening of the hydration. From the view of bond length, we can make a valid presumption that the site of negative charge will be the more preferable site of the hydration, and the preferable site may be changed because of the presence of other hydrogen bonds. Furthermore, we found that the first solvation shell had very little effect on the geometric structures except for the hydrogen bond P–O5···H5. By comparing the excitation energies, one important finding is that the changes in different electronic states are not obvious with the increase in n value when considering the PCM. Another finding is that the average interactions of hydrogen bonds may be strengthened with an increase of negative charge because of a decrease in excitation energies.

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