‘The discrete variable representation method for bound state eigenvalues and. eigenfunctions Frederico V, Prodemte, Antonio Rigateli, and 'Anténio LC. Varandas ‘Departamento de Quimica, Universidade de Couns P-3049 Coimbra Coder, Portal e-mail: !varandas@qres).quisie pt Recibido eM de mars de 201; acetal 25 de spice: de 201 The onc-shmcniol rail Shvdinger uations solved muerally by mens f the dsctete vandblerepesernion tod, Tiss bse arid epesetation ofthe quatar meson wavefunction diye nrhaod onthe sino igo vant! pieple. The ‘naa a Bs apliod wo he slcuion ofthe eneray spc of dc represenitve mi “gon particle moving ina guaic [neal Pansat ener levels of adiemnic mleele and ecru of hymn sn, ‘Kevwonds: Quantens mesa variational prefs bows sts: ces vale representation mtb Lace ail vidios de Sluinger x essks amdricanent pr med ch mab de aspect dyads {te mtn se sen fa epestaiin dea foi de onc Sobre uns ily pase seid iguana as el piiio ‘araconal, Hemos empleads dicho ated eno eeu del espe energies de tes models epesenativos: parte mes en ot ‘tenia suasc, ead enlzadon deo sola daisy expo ve inn J sem Desergtas: Mesinca cusses tipo viata: esos ekaados odo de reps de able Bereta PACS! 0270-60168 Ge: LISP “1, Introduetion ‘The sail Selwidinger equation ia second oder differential ‘ype equation thst arises inthe modeling of many physical Dhenowena at atomic seale: However, ths equation can be Solved analytically only for some simple potential movels ‘which ae normally encountered i textbooks of quantum re [1-3], Ths, the use of numerical methods to Schrédinger equation is fundamental for saying reslsic qusntum problems. These ean be either scaring ‘0 bound stat and resonance processes. In particular, the ‘nly of one-dimensional bound-state systems which wil be discussed here using the ine independent formalise present Seon inerest fon a pedagogical point of vies There ae {hee ain reasons fr this interest: ') The two-patiele processes are governed by oxe-d mensional Schebdinges equations. 1a) The method provides a relative simple introduction to the solution of many-dimensional probes, iti) Wsllows a pedagogical description of mumerial me- shod used in quantum mechanics Indeed, such an interest is corroborated by the aticles ‘which have appeared frm time Co time in educational jour- tals 1-12), ‘Numerical methods o solve one-dimensional eigenvalue problems eun be classified inte thre types: numerical int ‘rations (or shooting mestiods) (13,9 1}, matix or global approaches (11 15], and Rayleigh Ritz variational me thous (7, 10-18}. An approximate Rayleigh-Ritz variational ‘ethos demonssated high efficiency for solving ‘one-day -iemensona Schrodinger equation ‘ete variable representation (DVR) wethod (19,20). Tas ‘method was originally imeoducedt by Harris era (21) silly for evaluating potential matrix elements in the GD's. It was then by Dickinson and Cerain [22] shown to be related to ssi quadratire methods theoweh 3 snipe unitary trans formation. However it was only i the 80's that Light and co-workers [23-25] generalized the DVR method and applied ‘to a numberof interesting quantum mechanics! problems ‘An sdvantage ofthe DVR method is that its computer imple tation Is simple, Thi allows undergraduate students of ‘qu mechanical andlor coinputational physies courses to use sich a method sn a working tol to teat numerically ‘quant systems "This ability was shown 1 Be Very impor taut wien applied wo specific rexearch fields such as atom, molec and move recently solid state physics (26). Yet, 29 stele has appeared to dt ina eucational journal about the DVR method and its apliations. Inthe present work, swe aim to cover this gap by introducing the DVR. method froma pedagogical point of view. Since the emphasis willbe ‘on the computational technique and is physical justifeaion rather than onthe energy eigenvalue themselves, we apply the ‘method to thee well own prototypes in physies. First, we solve the rail Schrodinger equation fora guancum particle in an Rarmonic potential, Then, we use the same methodol ‘gy tocalelate the bound stats ofthe H molecule. Finally ‘ve caleulate energy spoctrun of the hydrogen atom. The ps pers oxpanizass follows tn Sec.2 we describe te genes! {hry of the DVI method, tile Sec. discusses the eqully spaced dssrete variable representation, The sppleations aft in Soc. 4. and he concluding remarks in See. 5.FREDERICOV.PRUDENTS ANTONIO RIGANELLL AND ANTONIO. VARANOAS 300 2. DVR method 2. Rayleigh Rite variational peiclple ‘The non-relativistic time independent radial Schringer ‘ation asumes in atomic units he for M+) Bu ‘where isthe reduced ass ofthe system, V(r) is he ntere ‘ston poten Ui the angular mementim quantum num ber Ee te energy egenvave, and U(r) is the corespond> ing wave function, Within the spc ofthe Rayleigh Ritz va onal principle te problem is wansformed nt that of fn ing dhe seionsy soltion ofthe functional J) given by wvhose Pe) = teh + (E+ 1)/2)r ke the fective po Sid Hath th tational ete To obtain mumescally the eigenenergies and eigenfunc- ions, the wave funtion is ist expanded using a fine basis tet {/,0)} which belongs toa L2-space: +¥E+ ie = Bair), a ae @ + Vein) B] 90. @ wid = Dah, o whste fey] ase de expansion coefcionts, Then, ig] is = {quired to be stationary onder variation of such eoelicien. ‘Thus. he variational procedure converts the probe ino that of solving «generalized eigenvalue problem, which in ix sotaton assumes tbe form “ were F o inthe vecworof eoefiients, aye me=-a ff engi) © sate kinetic energy max (T) elements, Ve de esting are pote entgy matin (V) eee i= [aroun ® are overlap mawix (S) elements In other words, the Ray> lejgh-Ritavadiacional procedure implies obtsining the eiges shies and eigenvectors of the geneclined eigenvalue peo- bem Eg. (4) Once the arsitonian matrix hasbeen Gul, the next cp wil Be to obtain its eigenvales, “Toe integras in Bs. (6) (7) and (8) ea sao be solved analyeally. For example, the potential energy matin ele rents (Eq (7) ean be obtained analytically ony for afew potnta models ae bass sets, This, & umetial sate f will be neces to calle sich integral. For proc> Teal resons the sembsnfinte ners of the eal coord rer € (Osco) has then tobe restricted to a inte ran rly € (eli). wheze we etume that ola) = 0) = O. Dar efciat way to evaluteonecinensonaterasis by wing the gaan quadetreechqee. which will bedi ‘hated in ext unetion, 22. Gaussian quadrature method Fora generat onecinensional ine tue formal sane the form (27.2 the gaussian quake [row= Somat whore drab a [er (oe = yoo) rete pos a Ireights whic define the gaan quadrature, especialy Each st of pivos and weights ascites toa pariulor set of bats fonctions g(r), (= Dy) which ae ‘etonormal inthe (8) ner, o Jaden, 0) [atoms ae= ay sch that the following orthogonality and completeness ions re satis: Least rads d= Do st lrade/?we! 4b a) stp «0D Latent nlrb elon Ke 2) 1 smportst opin out ha these sa unique se of points an weights hich salsy these elation foreach pate S58 of onhogonal polyomias (y,}- Using the Dire not tion (25) omy =, «3 id =, “ (iat) = f angie, as)570 THE DISCRETE VARIABLE REPRESENTATION METHOD FOR BOUND STATE BIGENVALUES AND EXGENFUNCTIONS sete h(e) sa vbirary function, we ean reve Eq. (01) nd (12) th or tal Sy lrobeaaid Llabraderatralan 4 09) Leet Meal DLirsly Madea = tra Sonn aot ayy From Bq, (16) anal (17) we can define the unit operaios in the coordinate representation and the projection operator for the {4,) space, respectively given by Tada al eb as) ane a Visdtos Equations (11) and (12) (or Eqs. (18) nd (19)] show there ove thatthe infinite and continuous representation of the space has been approximated by a fiite and discrete repre Ins easy 40 note that Eqs. (11) and (12) define an ortho= _gonaltnsformation, i {Uhia = 0H!" o0ra)> @o such that uty suuT =1%, en where 14 is the unity matrix of 1% K dimension. tn particu Tae Dickinson and Certain 22) demonstrated that this ortho ‘onal tansformation diagonalies the potential energy matin {in gener, any matrix representation ofthe coordinate ope ton) with the diagonal elements being given by the value of the potential energy at each qusdrature point Thus, the set of igaiesian quadrature points associated with the {g,} functions nay be taken as the eigenvalues ofa matrix (X) with A x fe tlimension the elements of which ae defined by bays | araterat where # is the position operator. However, the gaussian “quarature points are traditionally the roots ofthe yA?) ‘rvhonocinal funtion in dhe interval (u,b). In both case ae (quacirature weights are obtained from En, (12) doing «c= i ay ul7ig). " (Savane) wale C3 2.3, Discrete variable representation method ‘We discuss nest the general DVR method starting from the gaussian quadrature technique presented inthe previous see- tion. Consider puticlar gaussian quadrature with pi vous fry} and weights for]: a = Leeve-f6, The DVR trethod! consists of bulking a basis set which satisfies the conditions fated Kw tad were are the coefficients which depends on the particular quadrature choice [see Eq (293). and Prevnrieie 09 Using suet a buss to expand the wave function azeording to 165.G), one obtains 25) wins Sef =e “where the relation between the coeficiemts {¢, }and the va Tues ofthe wave Function on the pivots quadiatre {e(r,)} Renily obtained doing ¢= 1, in Ea, (26) and empioy- ing Bg, C21). Nove that the ave Huncion atthe quadraure point is directly evaksted from the eoeicents ofthe expan. fion abtained by solving the generalized eigenvalue problem, Eq. (4). “To obtain the basis function set (f} (a= .-++ fC) we expand it in’ teins of the “known functions gh fe ty «K) which satisfy Eqs, W012) = Del alfa) om where we have employe (19) The funtion gp) a Slved ac DVR primi function, To evalua te at ial Grif) we apply the gen qvdraure forma 5.) yielding = Seustesdalra) = eaatlraitas 8) where Ea, (24) fas aso been used. The constants Gent l= a,c of) cin now be calculated stxightfor- wordy from 8.25): or Male d= mame egboa 3)