Is there a minimum polarizability principle in chemical reactions?

被引:112
作者
Hohm, U [1 ]
机构
[1] Tech Univ Braunschweig, Inst Phys & Theoret Chem, D-38106 Braunschweig, Germany
关键词
D O I
10.1021/jp0014061
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
For complete fragmentations of the type A(m)B(n...) --> mA + nB + ... the change of the dipole polarizabilty Delta alpha = Sigma(i)nu(i)alpha(i) and its cube-root Delta alpha(CR) = Sigma(i)nu(i)alpha(i)(1/3) in as well as the atomization energy D-at are calculated from literature data (nu(i) is the stoichiometric coefficient). We have taken into account a large number of molecules containing the atoms H, C, N, O, S, P, F, Cl, Br, and I as well as the metals Fe and Os. The ranges of D-at and Sigma(i)nu(i)alpha(i) covered by the fragmentations are between 150 and 15 000 kJ mol(-1) and -6 and 170 x 10(-41) C-2 m(2) J(-1), respectively. In most cases Delta alpha > 0 is observed, whereas we always find Delta alpha(CR) > 0. Additionally, we observe a linear relationship D-at = A(mu) + B mu Sigma(i)nu(i)alpha(i)(u) between the atomization energy D-at and the sum of the dipole-polarizabilities of all chemical species taking part in the fragmentation. The linear relation is obtained for mu = 1 and 1/3. Our observation implies that the most stable isomer has the lowest polarizability and that in chemical reactions the most stable species (reactants or products) have the lowest sum of alpha(1/3).
引用
收藏
页码:8418 / 8423
页数:6
相关论文
共 39 条
[1]   Electric fields in ice and near water clusters [J].
Batista, ER ;
Xantheas, SS ;
Jónsson, H .
JOURNAL OF CHEMICAL PHYSICS, 2000, 112 (07) :3285-3292
[2]   THEORY OF THE LIGHT-FORCE TECHNIQUE FOR MEASURING POLARIZABILITIES [J].
BONIN, KD ;
KADARKALLEN, MA .
PHYSICAL REVIEW A, 1993, 47 (02) :944-960
[3]   ALKALI POLARIZABILITIES BY ATOMIC BEAM ELECTROSTATIC DEFLECTION METHOD [J].
CHAMBERLAIN, GE ;
ZORN, JC .
PHYSICAL REVIEW, 1963, 129 (02) :677-&
[4]   Correlation between hardness and activation energies for reactions of OH radical with halomethanes [J].
Chandra, AK ;
Uchimaru, T ;
Sugie, M ;
Sekiya, A .
CHEMICAL PHYSICS LETTERS, 2000, 318 (1-3) :69-74
[5]   Validity of the minimum polarizability principle in molecular vibrations and internal rotations:: An ab initio SCF study [J].
Chattaraj, PK ;
Fuentealba, P ;
Jaque, P ;
Toro-Labbé, A .
JOURNAL OF PHYSICAL CHEMISTRY A, 1999, 103 (46) :9307-9312
[6]   Static response properties of second-period atoms: coupled cluster calculations [J].
Das, AK ;
Thakkar, AJ .
JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 1998, 31 (10) :2215-2223
[7]   Structures, vibrational frequencies and polarizabilities of diazaborinines, triazadiborinines, azaboroles, and oxazaboroles [J].
Doerksen, RJ ;
Thakkar, AJ .
JOURNAL OF PHYSICAL CHEMISTRY A, 1999, 103 (13) :2141-2151
[8]   MEASUREMENT OF THE ELECTRIC POLARIZABILITY OF SODIUM WITH AN ATOM INTERFEROMETER [J].
EKSTROM, CR ;
SCHMIEDMAYER, J ;
CHAPMAN, MS ;
HAMMOND, TD ;
PRITCHARD, DE .
PHYSICAL REVIEW A, 1995, 51 (05) :3883-3888
[9]   A density functional approach to hardness, polarizability, and valency of molecules in chemical reactions [J].
Ghanty, TK ;
Ghosh, SK .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (30) :12295-12298
[10]   THE COMPLEX REFRACTIVE-INDEX (N)OVER CAP(SIGMA,T,RHO) OF NO2/N2O4 IN THE VISIBLE AND STATIC DIPOLE POLARIZABILITY OF N2O4 [J].
GOEBEL, D ;
HOHM, U ;
KERL, K ;
TRUMPER, U ;
MAROULIS, G .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (50) :13123-13130