A relativistic formalism to construct the Hamiltonian for a general N-electron neutral atom with a spin-1/2 nucleus and placed in a homogeneous magnetic field [J. Chem. Phys. 123 064101 (2005)] is discussed here. Projected Coulomb and Breit interactions are taken to describe the inter-particle interaction through second order in fine structure constant. The center of mass motion is separated from the movement of the neutral (N+1) fermion system. Using a series of suitable unitary transformations, the Hamiltonian can be brought into a separable form. The correct atomic Hamiltonian in the non-relativistic limit is also discussed. The treatment can be extended to the case of a molecule containing atoms of only spin-1/2 nuclei

Datta, Sambhu N

Misra, Anirban

IACS Institutional Repository

Indian J Phys. 81(9) 881-888(2007) $ Relativistic Hamiltonian for neutral atom of spin-1/2 nucleus in homogeneous magnetic field Anirban Misra Department of Chemistry, North Bengal University, Siligun Darjeeling-734 430 West Bengal India and Sambhu N Datta* Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 India Email sndatta<®chcm ntb ac in Abstract : A relativistic formalism to construct the Hamiltonian for a general N-electron neutral atom with a spin 1/2 nucleus and placed in a homogeneous magnetic field [J. Chem Phys 123 064101 (2005)] is discussed here Projected Coulomb and Breit interactions are taken to describe the inter-particle interaction through second order in fine structure constant The center of mass motion is separated from the movement of the neutral (/V+1)-fermion system Using a series of suitable unitary transformations, the Hamiltonian can be brought into a separable form The correct atomic Hamiltonian in the non-relativistic limit is also discussed The treatment can be extended to the case of a molecule containing atoms of only spin-Vfe nuclei Keywords : Relativistic Hamiltonian, projected interaction, non-relativistic limit PACS Nos. : 31 30 Jv, 31.30 jc, 31 30 jy, 12.20 Ds 1. Introduction In most of the state of art quantum theoretical calculations on atoms and molecules, one usually considers a faceless nucleus that provides only a Coulombic potential that can be legitimately viewed as an external one. Sometimes the effects of nuclear and electron spins are treated in a perturbative manner. However, for a multi-electron atom with a different nuclear spin, one can expect that there is a different form for the Hamiltonian operator. In our earlier work, the relativistic dynamics of one and two fermion systems placed in a homogeneous magnetic field were discussed in detail [1-3]. A generalization of this treatment has also been carried out explicitly [4]. In this work we describe the •Corresponding Author © 2007 IACS 882 Anirban Misra and Sambhu N Datta formulation of a relativistic Hamiltonian for a neutral N-electron atom with a spin-y2 nucleus in simpler terms. In Section 2 of this article, the phenomenological relativistic Hamiltonian is written for a (N+1) particle system with proper inter-particle electro-dynamical interaction [5]. In Section 3, the separation of the center of mass motion is carried out and the dynamics of each one-particle part is brought to a separable form. The non-relativistic Hamiltonian and a few general points of observation are discussed in Section 4. 2. Phenomenological Hamiltonian The total relativistic Hamiltonian for an atom with a spin-Vfe nucleus and N electrons, and placed in a homogeneous magnetic field, can be written from a generalized version [6] of the celebrated Bethe-Salpeter equation [7]. We write A/+1 X /-2 " = ^(nM+£M'U)+u d) where the first particle is the nucleus and rest N particles are electrons. The operator hD(i\r) is the Dirac Hamiltonian for the /-th particle, hD(i I r,) = ca, • /r, + j3,m,c2 - fiar)0(i)Pfa]2B. (2) In the above, m„ n, and juano(i) are the corresponding rest mass, operator for the mechanical momentum and the anomalous magnetic moment; B is magnetic field strength, and or„ /?, and a, are the respective Dirac matrices in standard representation The last term in the above equation arises from the interaction of the anomalous magnetic moment with the external magnetic field. We adopt the symmetric gauge here for convenience, that is, A(r) = Vz B x r,. The mechanical momentum is written as 7r, = p, — L A ( r l ) 1 where q, is the charge of the /-th particle. c The interaction U is taken as projected so that it can be used safely to all orders in perturbation theory, without fear from infinite degeneracy or continuum dissolution [5], U = A.(UB + UM)A+. (3) N In the above, / l + = f | A,+, k^ being the generalized Casimir projection operator, A„=5(l (+i»o(/") /£, ) (4) where E, is the diagonal form of h^i). The generalized Breit term UB is u = y q,q' i a,a> fc•*"«)•(*',r») Relativistic Hamiltonian for neutral atom of spin-1/2 nucleus in homogeneous magnetic field 883 where r„ = I /} - r, |, contains the retardation effect through order v2/c2. The magnetic interaction UM is the Barker-Glover generalization [8] of the interaction of the intrinsic magnetic moment with the external electromagnetic field, U» Mi V, 1£/</£A/+1 2/77,C r r », 2mjC riJ hi (6) 2/77 Q where/', =—r~AW)('') for / = 1, ..., A/+1. The quantity UM is not included in the treatment in Ref. [6]. 3. Simplification of dynamics The total relativistic Hamiltonian is expressed in a new set of coordinates, (f?CM> {r/}). The center of mass coordinate is defined by /V+1 " C M - Z-r * j '* ' and the relative coordinates are (7a) (7b) where MT is the total rest mass MT -~Zjm, , and r,' are defined for / = 2,..., /V+1. This allows one to write the Dirac Hamiltonian operators as [M; +/3,m1c2-/iaro(1)B/31CT1z, and for / = (2, N + 1), (8) (i) = cal-\-±K + pl--\ql(Acu + Al)-Z ' 4 The center of mass motion is also embedded in the relativistic Hamiltonian described in the previous section. The movement of the center of mass is separated from a 884 Anirban Misra and Sambhu N Datta neutral atom following the techniques put forward by Avron et al [9]. It is found that the total pseudo-momentum K = ]£ k, is a constant of motion for the Hamiltonian H, though the individual mechanical momentum n{ and individual pseudo-momentum K = P, + — A a r e not constants of motion. The components of K are found to satisfy c on the commutation relations KxK = -i—B where Q is the total charge written as A/+1 C ° = 2 9/ . These components are distinct only for a neutral atom. As JC commutes with H, one may replace the total pseudo-momentum K by its eigenvalue K [9]. This changes the Hamiltonian H(K) into the effective Hamiltonian H(K) and the projectors yl^(K) and A+(K) into the reduced projectors A,+(K) and A+{K). Using suitable unitary transformations one can transform the effective Hamiltonian into an exceedingly simple form. The translational motion for a neutral N-electron atom is discarded by considering the reduced Hamiltonian at zero total pseudo-momentum H(0) that represents the relative movements of the particles [4], «(0) = /6(1)+2/6(') + W(0). (9) 1=2 In the above /?o(1) = -ccc,g% k\ + P,m,c2 - /iano(1)e/Vx1z % (10) tfD(i) = ca,gn; + /5 , /n .c 2 - / v , (W, tv (for / = 2 A/), (11) and l/(0) = /UO)(l/B+tfMH<0) (12) with 4(0) = r K and A° =i|l+-3TT for '= 1 M-To gain certain advantages we bring first /fc(1) and then each /&(/) into a form that is separable for positive- and negative-energy states. In order to bring the Hamiltonian into a separable form, the odd Dirac matrices for the particles are replaced by even terms through the successive use of a set of Tsai [10] and Weaver [11] transformations, and one obtains the transformed one particle Hamiltonians as T1 /2 ^1/2 i*2 /«2 peiativistic Hamiltonian for neutral atom of spin-1/2 nucleus in homogeneous magnetic field 885 and M'') = A |1/2 n£cA + c2\ n* ~fe*\ -/W')/3r /z + c2p'* (13) where the r's are Pauli spin matrices. The transformed Dirac operators hT(f) are manifestly separable. To obtain their eigenvalues, one needs to substitute the eigenvalues of the z components individual mechanical momentum and of r1z in the above [2]. The above process also transforms the interaction operator. The odd terms in the transformed interaction can be removed by a series of Foldy-Wouthuysen type of transformations. The final form of the interaction operator becomes *^res = *^Bee "*" ^Darwin "** ^Darwin "*" ^ spin-orbit + ^spin-orbit +^correction "*" ^ hyperfine ^contact interaction + **hyperfme ( « 4 ) The components of the above interaction operator are explicitly given by t/Bee = - ^ E V - 1 + e 2 X V 1 . { Q i = _ KJ Ze) ,2fc2/ uDarwin Oir?C? ne2h2V + 2ne)-~ 2 3 2J ZJ5 (r«). mecr i >(>/) _ ^ 6 ^ ( 1 + 2 ^ ) V ' 3 "Darwin - « . J 2 „ 2 ZJ ° \'l >• _Ze2fr1 + 2 ^ ) y ' r,' "sptn-orbtt 7 1 X 5 2 ^ 2 * a < r>3Xpl + , - i J 2 - 2 - ai ^3xPi< 886 Anirban Misra and Sambhu N Datta ^correct™ = ~ „ . , * » X £ 17' t f" Pi + ^ 3 ' / C r P',)-Pl\ 2Mmec , i [r, v s ' l 7";'p;4w'p;)'p; • 2/n|c2 T /~> I r„ U, hyperfine 4me<f , ,(>,)[ rn rv U, 2ne2h*(\ + ne)2 contact Interaction —j3, L Lar°,° Ci). 3mec , /<>,) Ze2fif 1 + 2/1, 2(1 + ^ ) 1 4cz M' Mma vE'4 xp, + Ze2ft 4M2c2 (15) The prime on each summation sign indicates that summations are taken for / = 2, ., N +1. The genesis of the above terms is very clear from this treatment that is discussed in detail in Ref. [4]. Most of these terms are well known. However, the third and the last term in the above, U'Darwin and l/'Hyperf.ne. are not commonly encountered in the literature, are lower than the respective unprimed terms by factors of m%IM2 and mJM respectively, and will need attention as more powerful experimental techniques develop. 4. Discussion Most of the systems of interest in Chemistry are weakly relativistic. With a few exceptions like nuclear spins that control NMR, and X-ray spectroscopy, most of the chemical effects are in the non-relativistic limits. Therefore, one would like to know the non-relativistic limit of the transformed Hamiltonian. The Hamiltonian in the non-relativistic limit is obtained by expanding the one-particle operators hT(iYs through order v2/c2, and replacing the transformed Casimir projection operators by unit operators. We get 'nonrel = W U + AW~ + WEDr + 4WEDr + WNmr + W^ + U' . Epr rNmr 'rel (16) In the non-relativistic Hamiltonian, W ^ is the Schrodinger free-particle Hamiltonian, and Relativistic Hamiltonian for neutral atom of spin-1/2 nucleus in homogeneous magnetic field 887 AWSCh is a corrective term due to the nuclear recoil, IVEpr is the interaction of the magnetic field with the total orbital angular momentum and the total spin angular momentum of the electrons and the diamagnetic interactions, the term AWEpr represents the interaction of the orbital angular momentum of the recoiling nucleus with the magnetic field. The term WNmr is for the energy of interaction of the nuclear spin magnetic moment and the magnetic field, and IV^, is the kinetic energy corrections. These contributions, are explicitly written as Here, L and S are the total orbital angular momentum and the total spin angular momentum operators for the electrons, and / is the spin angular momentum operator for the nucleus. This theory has the following accomplishments : (1) The nuclear magnetic resonance and electron paramagnetic resonance interaction terms have been derived here from the appropriate relativistic Hamiltonian for an all-fermion atom placed in a homogeneous magnetic field. (2) The correction term to electron paramagnetic resonance is generally not considered in literature. However, its effect would be of the order of hyperfine interactions and hence must be accounted for in an accurate analysis of the EPR spectrum. (3) Its effect should also be detected in NMR spectroscopy for a L * 0 atom. As a whole, we observe that Tsai and Weaver transformations can be systematically applied to derive the N-electron Hamiltonian for an atom with a spin-12 nucleus. It is possible to rigorously derive the transformed Hamiltonian which is separable for individual positive- and negative-energy states for all the particles, specifically here through order \P/c2 in interaction. The non-relativistic limit of the 888 AnirbanMisra andSambhuN Datta transformed Hamiltonian is easily calculated. From this, the origin of the electronic and magnetic resonance spectroscopies can be explained. Although the treatment here is for an all-fermion atom, it can easily be extended to the treatment of a molecule containing only the spin-te nuclei. In the latter case, particles 2, 3, etc. will be considered as nuclei, and the rest as electrons. The center of mass needs to be redefined. The operator W^ has to be modified, and one will have to apply a careful accounting of the dynamics while taking the Bom-Oppenheimer approximation and the non-adiabatic coupling into considerations. This part of the work remains to be done. We have recently derived the expression for the retarded interaction between a spin-0 boson and a spin-1/2 fermion [12]. This derivation opens up the possibility of writing the Hamiltonian operator for a general molecule that consists of spin-0 and spin-1/2 nuclei, like carbon, oxygen, and of course, hydrogen. Acknowledgment AM and SND are grateful for financial support from DST and CSIR respectively. References [1] S N Datta and A Misra J. Chem. Phys. 114 1478 (2001); ibid. 114 9209 (2001) [2] S N Datta and A Misra Int. J. Quantum Chem. 82 209 (2001) [3] S N Datta and A Misra Int. J. Quantum Chem. 90 812 (2002) [4] A Misra and S N Datta J. Chem. Phys. 123 064101 (2005) [5] J Sucher Phys. Rev. A22 348 (1980) [6] I Lindgren, S Salomonson and B As6n Phys. Reports 389161 (2004); I Lindgren, S Salomonson and D Hedendahl Phys. Rev. A73 056501 (2006) (71 E E Salpeter and H A Bethe Phys. Rev. 841232 (1951) [8] W A Barker and F N Glover Phys. Rev. 99 317 (1955) [9] J E Avron, I W Herbst and B Simon Ann. Phys. (New York) 114 431 (1978) [10] W Tsai Phys. Rev. D71945 (1973) [11] D L Weaver J. Math. Phys. 18 306 (1977) [12] S N Datta and A Misra J. Chem. Phys. 125 084111 (2006) 

Relativistic Hamiltonian for Neutral Atom of Spin-1/2 Nucleus in Homogeneous Magnetic Field

MISRA, A

DATTA, SN

Dspace at IIT Bombay

Relativistic Hamiltonian for neutral atom of spin-1/2 nucleus in homogeneous magnetic field

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Relativistic Hamiltonian for Neutral Atom of Spin-1/2 Nucleus in Homogeneous Magnetic Field

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