Full-dimensional adiabatic potential energy surfaces of the electronic ground state X and nine excited states A,I,B,C,D,D',D'',E' and F of H_(2)O molecule are developed at the level of internally contr...Full-dimensional adiabatic potential energy surfaces of the electronic ground state X and nine excited states A,I,B,C,D,D',D'',E' and F of H_(2)O molecule are developed at the level of internally contracted multireference configuration interaction with the Davidson correction.The potential energy surfaces are fitted by using Gaussian process regression combining permutation invariant polynomials.With a large selected active space and extra diffuse basis set to describe these Rydberg states,the calculated vertical excited energies and equilibrium geometries are in good agreement with the previous theoretical and experimental values.Compared with the well-investigated photodissociation of the first three low-lying states,both theoretical and experimental studies on higher states are still limited.In this work,we focus on all the three channels of the highly excited state,which are directly involved in the vacuum ultraviolet photodissociation of water.In particular,some conical intersections of D-E',E'-F,A-I and I-C states are clearly illustrated for the first time based on the newly developed potential energy surfaces(PESs).The nonadiabatic dissociation pathways for these excited states are discussed in detail,which may shed light on the photodissociation mechanisms for these highly excited states.展开更多
This paper reviews sulfur-induced passivity degradation of nuclear materials with emphasis on steam generator(SG)alloys. The state of arts on this topic concerning thermodynamic calculation and experimental data has b...This paper reviews sulfur-induced passivity degradation of nuclear materials with emphasis on steam generator(SG)alloys. The state of arts on this topic concerning thermodynamic calculation and experimental data has been reviewed. Thermodynamic calculation results indicate that the distribution of sulfur species strongly depends on p H and temperature. Experimental data show that solution p H, temperature and solution chemistries can significantly affect the electrochemical behaviors of SG materials and the underlying degradation mechanisms. Some issues when conducting corrosion tests at high temperature should be paid attention to, such as the dissolution of the autoclave, which may affect the facticity of the experimental results.展开更多
The photodissociation of Br2 was investigated within the near-visible UV absorption band. Based on the potential curves for the ground and low-lying excited states, the optical cross-sections for the discrete transiti...The photodissociation of Br2 was investigated within the near-visible UV absorption band. Based on the potential curves for the ground and low-lying excited states, the optical cross-sections for the discrete transitions of C1^Пu,B^3Пou^＋, A^3П1u←X^1∑g＋ and their total energy absorption spectrum are derived, and the quantum yield of （Br＋Br6＊） channel are determined correspondingly. The one-dimensional Landau-Zener model is used to evaluate the behavior of curve crossing during photodissociation. The results indicate that the influence of nonadiabatic mechanism, which may be caused by the electronic-vibrational interplay between the 13 and C states, is negligibly small for the （Br＋Br^＊） channel. From the Landau-Zener modeling of the observed product recoil parameter β（Br＋Br）, the best-fit value of the coupling matrix elenment or coupling strength between the diabatic B and C state potentials is obtained.展开更多
Affected by structural uplift, the Ordovician carbonate rockbed in the Tarim Basin, China, was exposed to dissolution and reformation of atmospheric precipitation many times, and formed a large quantity of karst caves...Affected by structural uplift, the Ordovician carbonate rockbed in the Tarim Basin, China, was exposed to dissolution and reformation of atmospheric precipitation many times, and formed a large quantity of karst caves serving as hydrocarbon reser- voir. However, drilling in Tahe area showed that many large karst caves, small pores and fractures are filled by calcite, result- ing in decrease in their reservoir ability. Calcite filled in the karst caves has very light oxygen isotopic composition and STSr/S（＇Sr ratio. Its c^OpDB ranges from -21.2%o to 13.3%o with the average of -16.3%e and its 87Sr/86Nr ratio ranges from 0.709561 to 0.710070 with the average of 0.709843. The isotope composition showed that calcite is related to atmospheric precipitation. Theoretic analyses indicated that the dissolving and filling actions of the precipitation on carbonate rocks are controlled by both thermodynamic and kinetic mechanisms. Among them, the thermodynamic factor determines that the pre- cipitation during its flow from the earth surface downward plays important roles on carbonate rocks from dissolution to satura- tion, further sedimentation, and finally filling. In other words, the depth of the karstification development is not unrestricted, but limited by the precipitation beneath the earth surface. On the other hand, the kinetic factor controls the intensity, depth, and breadth of the karstification development, that is, the karstification is also affected by topographic, geomorphologic, climatic factors, the degree of fracture or fault, etc. Therefore, subject to their joint effects, the karstification of the precipitation on the Ordovician carbonate rocks occurs only within a certain depth （most about 200 m） under the unconformity surface, deeper than which carbonate minerals begin to sedimentate and fill the karst caves that were formed previously.展开更多
基金supported by the National Natural Science Foundation of China(No.12047532,No.21733006,No.22073042,and No.22122302)。
文摘Full-dimensional adiabatic potential energy surfaces of the electronic ground state X and nine excited states A,I,B,C,D,D',D'',E' and F of H_(2)O molecule are developed at the level of internally contracted multireference configuration interaction with the Davidson correction.The potential energy surfaces are fitted by using Gaussian process regression combining permutation invariant polynomials.With a large selected active space and extra diffuse basis set to describe these Rydberg states,the calculated vertical excited energies and equilibrium geometries are in good agreement with the previous theoretical and experimental values.Compared with the well-investigated photodissociation of the first three low-lying states,both theoretical and experimental studies on higher states are still limited.In this work,we focus on all the three channels of the highly excited state,which are directly involved in the vacuum ultraviolet photodissociation of water.In particular,some conical intersections of D-E',E'-F,A-I and I-C states are clearly illustrated for the first time based on the newly developed potential energy surfaces(PESs).The nonadiabatic dissociation pathways for these excited states are discussed in detail,which may shed light on the photodissociation mechanisms for these highly excited states.
基金Supported by the National Basic Research Program of China("973"Program,No.2014CB046805)National Natural Science Foundation of China(No.51131007,No.51371124)+1 种基金Natural Science Foundation of Tianjin(No.14JCYBJC17700)the Open-Ended Fund of the Key Laboratory of Nuclear Materials and Safety Assessment(Institute of Metal Research,Chinese Academy of Sciences,China)(No.2016NMSAKF02)
文摘This paper reviews sulfur-induced passivity degradation of nuclear materials with emphasis on steam generator(SG)alloys. The state of arts on this topic concerning thermodynamic calculation and experimental data has been reviewed. Thermodynamic calculation results indicate that the distribution of sulfur species strongly depends on p H and temperature. Experimental data show that solution p H, temperature and solution chemistries can significantly affect the electrochemical behaviors of SG materials and the underlying degradation mechanisms. Some issues when conducting corrosion tests at high temperature should be paid attention to, such as the dissolution of the autoclave, which may affect the facticity of the experimental results.
基金ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.10534010 and No.20673140）.
文摘The photodissociation of Br2 was investigated within the near-visible UV absorption band. Based on the potential curves for the ground and low-lying excited states, the optical cross-sections for the discrete transitions of C1^Пu,B^3Пou^＋, A^3П1u←X^1∑g＋ and their total energy absorption spectrum are derived, and the quantum yield of （Br＋Br6＊） channel are determined correspondingly. The one-dimensional Landau-Zener model is used to evaluate the behavior of curve crossing during photodissociation. The results indicate that the influence of nonadiabatic mechanism, which may be caused by the electronic-vibrational interplay between the 13 and C states, is negligibly small for the （Br＋Br^＊） channel. From the Landau-Zener modeling of the observed product recoil parameter β（Br＋Br）, the best-fit value of the coupling matrix elenment or coupling strength between the diabatic B and C state potentials is obtained.
基金sponsored by the National Basic Research Program of China(Grant No.2012CB214802)National Natural Science Foundation of China(Grant Nos.41002037,41102075,41230312)
文摘Affected by structural uplift, the Ordovician carbonate rockbed in the Tarim Basin, China, was exposed to dissolution and reformation of atmospheric precipitation many times, and formed a large quantity of karst caves serving as hydrocarbon reser- voir. However, drilling in Tahe area showed that many large karst caves, small pores and fractures are filled by calcite, result- ing in decrease in their reservoir ability. Calcite filled in the karst caves has very light oxygen isotopic composition and STSr/S（＇Sr ratio. Its c^OpDB ranges from -21.2%o to 13.3%o with the average of -16.3%e and its 87Sr/86Nr ratio ranges from 0.709561 to 0.710070 with the average of 0.709843. The isotope composition showed that calcite is related to atmospheric precipitation. Theoretic analyses indicated that the dissolving and filling actions of the precipitation on carbonate rocks are controlled by both thermodynamic and kinetic mechanisms. Among them, the thermodynamic factor determines that the pre- cipitation during its flow from the earth surface downward plays important roles on carbonate rocks from dissolution to satura- tion, further sedimentation, and finally filling. In other words, the depth of the karstification development is not unrestricted, but limited by the precipitation beneath the earth surface. On the other hand, the kinetic factor controls the intensity, depth, and breadth of the karstification development, that is, the karstification is also affected by topographic, geomorphologic, climatic factors, the degree of fracture or fault, etc. Therefore, subject to their joint effects, the karstification of the precipitation on the Ordovician carbonate rocks occurs only within a certain depth （most about 200 m） under the unconformity surface, deeper than which carbonate minerals begin to sedimentate and fill the karst caves that were formed previously.
