Nano-Y_2O_3:Eu^(3+) powder was prepared by the homogeneous precipitation. With controlling the conditions of the reaction, nano powders with different grain size were obtained. It is found that the blue-shift phenomen...Nano-Y_2O_3:Eu^(3+) powder was prepared by the homogeneous precipitation. With controlling the conditions of the reaction, nano powders with different grain size were obtained. It is found that the blue-shift phenomena exist in the nano-Y2O3:Eu3+ emission spectra excited by X-ray. The wave lengths of the peak (5D0→7F2) are related with the grain size of the powder展开更多
Theoretical calculations are performed to study the nature of the hydrogen bonds in complexes HCHO···HNO, HCOOH···HNO, HCHO···NH3, HCOOH···NH3, HCHO·...Theoretical calculations are performed to study the nature of the hydrogen bonds in complexes HCHO···HNO, HCOOH···HNO, HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F. The geomet- ric structures and vibrational frequencies of these six complexes at the MP2/6-31+G(d,p), MP2/6-311++G(d,p), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels are calculated by standard and counterpoise-corrected methods, respectively. The results indicate that in complexes HCHO···HNO and HCOOH···HNO the N—H bond is strongly contracted and N—H···O blue-shifted hydrogen bonds are observed. While in complexes HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F, the N—H bond is elongated and N—H···O red-shifted hydrogen bonds are found. From the natural bond orbital analysis it can be seen that the X—H bond length in the X—H···Y hydrogen bond is controlled by a balance of four main factors in the opposite directions: hyperconjugation, electron density redistribu- tion, rehybridization and structural reorganization. Among them hyperconjugation has the effect of elongating the X—H bond, and the other three factors belong to the bond shortening effects. In complexes HCHO···HNO and HCOOH···HNO, the shortening effects dominate which lead to the blue shift of the N—H stretching frequencies. In complexes HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F where elongating effects are dominant, the N—H···O hydrogen bonds are red-shifted.展开更多
Ab initio quantum chemistry methods were applied to study the bifurcated bent hydrogen bonds Y… H2CZ (Z = O, S, Se) and Y…H2CZ2 (Z = F, Cl, Br) (Y = Cl-, Br-) at the MP2/6-311++G(d,p) and MP2/6-311++G(2df,2p) levels...Ab initio quantum chemistry methods were applied to study the bifurcated bent hydrogen bonds Y… H2CZ (Z = O, S, Se) and Y…H2CZ2 (Z = F, Cl, Br) (Y = Cl-, Br-) at the MP2/6-311++G(d,p) and MP2/6-311++G(2df,2p) levels. The results show that in each complex there are two equivalent blue-shifted H-bonds Y…H—C, and that the interaction energies and blue shifts are large, the energy of each Y…H—C H-bond is 15-27 kJ/mol, and Δr(CH) = -0.1 - -0.5 pm and Δv(CH) = 30 - 80 cm-1. The natural bond orbital analysis shows that these blue-shifted H-bonds are caused by three factors: large rehybridization; small direct intermolecular hyperconjugation and larger indirect intermolecular hy- perconjugation; large decrease of intramolecular hyperconjugation. The topological analysis of elec- tron density shows that in each complex there are three intermolecular critical points: there is one bond critical point between the acceptor atom Y and each hydrogen, and there is a ring critical point inside the tetragon YHCH, so these interactions are exactly H-bonding.展开更多
A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric s...A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric structures and vibrational frequencies at the MP2/6-31G（d）, MP2/6-31 ＋ G（d,p）, MP2/6-311 ＋ ＋ G（d,p）, B3LYP/6-31G（d）, B3LYP/6-31 ＋G（d,p） and B3LYP/6-311 ＋ ＋G（d,p） levels. In the H-bond N-H…O, the calculated blue shift of N-H stretching frequency is in the vicinity of 120 cm^-1 and this is indeed the largest theoretical estimate of a blue shift in the X-H…Y H-bond ever reported in the literature. From the natural bond orbital analysis, the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation. For the blue-shifted H-bond N-H…O, the hyperconjugation was inhibited due to the existence of significant electron density redistribution effect, and the large blue shift of the N-H stretching frequency was prominently due to the rehybridization of spn N-H hybrid orbital.展开更多
MP2/6-31 + g(d) calculations were performed verifying the existences ofblue-shifting X - C ≡ C - CF_2 - H···OH_2 hydrogen bonds. Detailed analyses revealed that theinteraction energy and donor-acceptor...MP2/6-31 + g(d) calculations were performed verifying the existences ofblue-shifting X - C ≡ C - CF_2 - H···OH_2 hydrogen bonds. Detailed analyses revealed that theinteraction energy and donor-acceptor distance had good correlations with the substituent Hammettconstants. However, the extent of C―H bond contraction and the blue shift of the C―H stretchingvibration did not show any good correlation with the traditional substituent constants, indicatingthat certain more complicated mechanisms might be involved in the present systems. Nevertheless, itwas found that highly electron-withdrawing susbtituents were not favorable to the C―H bondcontraction, and it was suggested that the attractive interaction between water and the carbon of -CF_2H probably played an important role in the blue shift.展开更多
文摘Nano-Y_2O_3:Eu^(3+) powder was prepared by the homogeneous precipitation. With controlling the conditions of the reaction, nano powders with different grain size were obtained. It is found that the blue-shift phenomena exist in the nano-Y2O3:Eu3+ emission spectra excited by X-ray. The wave lengths of the peak (5D0→7F2) are related with the grain size of the powder
基金the National Natural Science Foundation of China(Grant No.20477043)Knowledge Innovation Program by Chinese Academy of Sciences(KJCX2-SW-H08)
文摘Theoretical calculations are performed to study the nature of the hydrogen bonds in complexes HCHO···HNO, HCOOH···HNO, HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F. The geomet- ric structures and vibrational frequencies of these six complexes at the MP2/6-31+G(d,p), MP2/6-311++G(d,p), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels are calculated by standard and counterpoise-corrected methods, respectively. The results indicate that in complexes HCHO···HNO and HCOOH···HNO the N—H bond is strongly contracted and N—H···O blue-shifted hydrogen bonds are observed. While in complexes HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F, the N—H bond is elongated and N—H···O red-shifted hydrogen bonds are found. From the natural bond orbital analysis it can be seen that the X—H bond length in the X—H···Y hydrogen bond is controlled by a balance of four main factors in the opposite directions: hyperconjugation, electron density redistribu- tion, rehybridization and structural reorganization. Among them hyperconjugation has the effect of elongating the X—H bond, and the other three factors belong to the bond shortening effects. In complexes HCHO···HNO and HCOOH···HNO, the shortening effects dominate which lead to the blue shift of the N—H stretching frequencies. In complexes HCHO···NH3, HCOOH···NH3, HCHO···NH2F and HCOOH···NH2F where elongating effects are dominant, the N—H···O hydrogen bonds are red-shifted.
文摘Ab initio quantum chemistry methods were applied to study the bifurcated bent hydrogen bonds Y… H2CZ (Z = O, S, Se) and Y…H2CZ2 (Z = F, Cl, Br) (Y = Cl-, Br-) at the MP2/6-311++G(d,p) and MP2/6-311++G(2df,2p) levels. The results show that in each complex there are two equivalent blue-shifted H-bonds Y…H—C, and that the interaction energies and blue shifts are large, the energy of each Y…H—C H-bond is 15-27 kJ/mol, and Δr(CH) = -0.1 - -0.5 pm and Δv(CH) = 30 - 80 cm-1. The natural bond orbital analysis shows that these blue-shifted H-bonds are caused by three factors: large rehybridization; small direct intermolecular hyperconjugation and larger indirect intermolecular hy- perconjugation; large decrease of intramolecular hyperconjugation. The topological analysis of elec- tron density shows that in each complex there are three intermolecular critical points: there is one bond critical point between the acceptor atom Y and each hydrogen, and there is a ring critical point inside the tetragon YHCH, so these interactions are exactly H-bonding.
基金Project supported by the National Natural Science Foundation of China （No. G20477043） and Knowledge Creative Program of Chinese Academy of Sciences （No. KJCX2-SW-H08）.
文摘A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric structures and vibrational frequencies at the MP2/6-31G（d）, MP2/6-31 ＋ G（d,p）, MP2/6-311 ＋ ＋ G（d,p）, B3LYP/6-31G（d）, B3LYP/6-31 ＋G（d,p） and B3LYP/6-311 ＋ ＋G（d,p） levels. In the H-bond N-H…O, the calculated blue shift of N-H stretching frequency is in the vicinity of 120 cm^-1 and this is indeed the largest theoretical estimate of a blue shift in the X-H…Y H-bond ever reported in the literature. From the natural bond orbital analysis, the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation. For the blue-shifted H-bond N-H…O, the hyperconjugation was inhibited due to the existence of significant electron density redistribution effect, and the large blue shift of the N-H stretching frequency was prominently due to the rehybridization of spn N-H hybrid orbital.
文摘MP2/6-31 + g(d) calculations were performed verifying the existences ofblue-shifting X - C ≡ C - CF_2 - H···OH_2 hydrogen bonds. Detailed analyses revealed that theinteraction energy and donor-acceptor distance had good correlations with the substituent Hammettconstants. However, the extent of C―H bond contraction and the blue shift of the C―H stretchingvibration did not show any good correlation with the traditional substituent constants, indicatingthat certain more complicated mechanisms might be involved in the present systems. Nevertheless, itwas found that highly electron-withdrawing susbtituents were not favorable to the C―H bondcontraction, and it was suggested that the attractive interaction between water and the carbon of -CF_2H probably played an important role in the blue shift.
