is qmc delivering its early promises? dario bressanini qmci sardagna (trento) 2006 universita’...

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Is QMC delivering its early promises? Is QMC delivering its early promises? Dario Dario Bressanini Bressanini QMCI Sardagna QMCI Sardagna ( ( Trento Trento ) ) 2006 2006 http://scienze-como.uninsubria.it/ http://scienze-como.uninsubria.it/ bressanini bressanini Universita’ dell’Insubria, Como, Italy Universita’ dell’Insubria, Como, Italy Some reflections on nodes and trial wave function Some reflections on nodes and trial wave function

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Page 1: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

Is QMC delivering its early promises?Is QMC delivering its early promises?Dario Dario BressaniniBressanini

QMCI Sardagna QMCI Sardagna ((TrentoTrento) ) 2006 2006

http://scienze-como.uninsubria.it/http://scienze-como.uninsubria.it/bressaninibressanini

Universita’ dell’Insubria, Como, ItalyUniversita’ dell’Insubria, Como, Italy

Some reflections on nodes and trial wave functionsSome reflections on nodes and trial wave functions

Page 2: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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30 years of QMC in 30 years of QMC in chemistrychemistry

Page 3: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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The Early promises?The Early promises?

Solve the Schrödinger equation Solve the Schrödinger equation exactly exactly withoutwithout approximationapproximation (very strong)(very strong)

Solve the Schrödinger equation with Solve the Schrödinger equation with controlled approximationscontrolled approximations, and converge , and converge to the exact solution to the exact solution (strong)(strong)

Solve the Schrödinger equation with Solve the Schrödinger equation with some some approximationapproximation, and do better than other , and do better than other methods methods (weak)(weak)

Page 4: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Good for Helium studiesGood for Helium studies

ThousandsThousands of theoretical and experimental of theoretical and experimental paperspapers

)()(ˆ RR nnn EH )()(ˆ RR nnn EH

have been published on Helium, in its various forms:have been published on Helium, in its various forms:

AtomAtom Small ClustersSmall Clusters DropletsDroplets BulkBulk

Page 5: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

5

33HeHemm44HeHenn Stability Chart Stability Chart

3232

44HeHenn 33HeHemm 0 1 2 3 4 5 6 70 1 2 3 4 5 6 7 8 9 10 11 8 9 10 11

00

11

22

33

44

55

33HeHe3344HeHe88 L=0 S=1/2 L=0 S=1/2

33HeHe2244HeHe44 L=1 S=1 L=1 S=1

33HeHe2244HeHe22 L=0 S=0 L=0 S=0

33HeHe3344HeHe44 L=1 S=1/2 L=1 S=1/2

Terra IncognitaTerra IncognitaTerra IncognitaTerra Incognita

Bound L=0Bound L=0

UnboundUnbound

UnknownUnknown

L=1 S=1/2L=1 S=1/2

L=1 S=1L=1 S=1

BoundBound

Page 6: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Good for vibrational Good for vibrational problemsproblems

Page 7: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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For electronic structure?For electronic structure?

Sign ProblemSign Problem

Fixed Nodal error problemFixed Nodal error problem

Page 8: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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The influence on the nodes The influence on the nodes of of

QMC currently relies on QMC currently relies on TT(R)(R) and its nodes and its nodes

((indirectlyindirectly))

How are the nodes How are the nodes TT(R)(R) of influenced by: of influenced by: The single particle basis setThe single particle basis set The generation of the orbitals (HF, CAS, MCSCF, NO, The generation of the orbitals (HF, CAS, MCSCF, NO,

…)…) The number and type of configurations in the multidet. The number and type of configurations in the multidet.

expansionexpansion ??

Page 9: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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HeHe22++: the basis set: the basis set

)2())1()3()3()1(()( gugugRHF R )2())1()3()3()1(()( gugugRHF R

The ROHF wave function:The ROHF wave function:

1s1s

E = -4.99E = -4.990505(2) hartree(2) hartree1s1s’2s3s1s1s’2s3s

E = -4.99E = -4.994343(2) hartree(2) hartree

EEN.R.LN.R.L = -4.99 = -4.994545 hartree hartree

Page 10: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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HeHe22++: MO’s: MO’s

E(RHF) = -4.99E(RHF) = -4.994343(2) (2) hartreehartree

E(CAS) = -4.99E(CAS) = -4.992525(2) (2) hartreehartree

E(CAS-NO) = -4.99E(CAS-NO) = -4.991616(2) (2) hartreehartree

E(CI-NO) = -4.99E(CI-NO) = -4.991717(2) (2) hartreehartree

EEN.R.LN.R.L = -4.99 = -4.994545 hartree hartree

Bressanini et al. J. Chem. Phys. 123, 204109 (2005) Bressanini et al. J. Chem. Phys. 123, 204109 (2005)

Page 11: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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HeHe22++: CSF’s: CSF’s

1s1s’2s3s2p2p’1s1s’2s3s2p2p’

E(1 csf) = -4.99E(1 csf) = -4.993232(2) hartree(2) hartree

1s1s’2s3s1s1s’2s3s

E(1 csf) = -4.99E(1 csf) = -4.994343(2) hartree(2) hartree

+ +

E(2 csf) = -4.99E(2 csf) = -4.994646(2) hartree(2) hartree

2121 1111 uyuuxu 2121 1111 uyuuxu

+ +

E(2 csf) = -4.99E(2 csf) = -4.992525(2) hartree(2) hartree

111 211 gug 111 211 gug

Page 12: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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LiLi22

-14.9954 E (N.R.L.)E (N.R.L.)

-14.9952(1)

-14.9939(2)

-14.9933(1)

-14.9933(2)

-14.9914(2)

-14.9923(2)

E (hartree) CSF22 g

222 9...43 ggg 22 11 uyux

224 uyux nn 222 211 uuyux

2222 3211 guuyux

Not all CSF are usefulNot all CSF are useful Only 4 csf are needed to build a statistically Only 4 csf are needed to build a statistically

exact nodal surfaceexact nodal surface

(1(1gg22 1 1uu

22 omitted) omitted)

Page 13: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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A tentative recipeA tentative recipe Use a large Slater basisUse a large Slater basis

But not too largeBut not too large Try to reach HF Try to reach HF nodesnodes convergence convergence

Orbitals from CAS Orbitals from CAS seemseem better than HF, or NO better than HF, or NO Not worth optimizing MOs, if the basis is large Not worth optimizing MOs, if the basis is large

enoughenough Only few configurationsOnly few configurations seem to improve the FN seem to improve the FN

energyenergy Use the right determinants...Use the right determinants...

...different Angular Momentum CSFs...different Angular Momentum CSFs

And not the bad onesAnd not the bad ones ...types already included...types already included

222234

222234

222234

31)31(ˆ

21)21(ˆ

21)21(ˆ

ssssi

pspsi

ssssi

222234

222234

222234

31)31(ˆ

21)21(ˆ

21)21(ˆ

ssssi

pspsi

ssssi

Page 14: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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DimersDimers

Bressanini et al. J. Chem. Phys. 123, 204109 (2005) Bressanini et al. J. Chem. Phys. 123, 204109 (2005)

Page 15: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Is QMC competitive ?Is QMC competitive ?

Page 16: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Carbon Atom: EnergyCarbon Atom: Energy CSFsCSFs Det.Det. EnergyEnergy 1 1 1s1s222s2s2 2 2p2p2211 -37.8303(4)-37.8303(4) 2 2 + 1s+ 1s22 2p 2p44 22 -37.8342(4)-37.8342(4) 5 5 + 1s+ 1s22 2s 2s 2p2p223d3d 1818 -37.8399(1)-37.8399(1) 83 83 1s1s22 + 4 electrons in + 4 electrons in 2s 2p 3s 3p 3d2s 2p 3s 3p 3d shell shell

422422 -37.8387(4)-37.8387(4)

adding f orbitalsadding f orbitals 77 (4f(4f22 + 2p + 2p334f)4f) 3434 -37.8407(1)-37.8407(1)

R12-MR-CIR12-MR-CI -37.845179-37.845179ExactExact (estimated) (estimated) -37.8450-37.8450

Page 17: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Ne AtomNe Atom

Drummond Drummond et al. et al. -128.9237(2) -128.9237(2) DMCDMCDrummond Drummond et al. et al. -128.9290(2) -128.9290(2) DMC backflowDMC backflowGdanitz Gdanitz et al. et al. -128.93701 -128.93701 R12-MR-CIR12-MR-CIExact (estimated)Exact (estimated) -128.9376-128.9376

Page 18: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Conventional wisdom on Conventional wisdom on

EEVMCVMC((RHFRHF) > E) > EVMCVMC((UHFUHF) > E) > EVMCVMC((GVBGVB))

Single particle approximationsSingle particle approximations

RHFRHF = = |1s|1sRR 2s 2sRR 2p 2pxx 2p 2pyy 2p 2pzz| |1s| |1sRR 2s 2sRR||

UHFUHF = = |1s|1sUU 2s 2sUU 2p 2pxx 2p 2pyy 2p 2pzz| |1s’| |1s’UU 2s’ 2s’UU||

Consider the Consider the NN atom atom

EEDMCDMC((RHFRHF) ) > ? <> ? < E EDMCDMC((UHFUHF))

Page 19: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Conventional wisdom on Conventional wisdom on

We can build a We can build a RHFRHF with the same nodes of with the same nodes of UHFUHF

UHFUHF = = |1s|1sUU 2s 2sUU 2p 2pxx 2p 2pyy 2p 2pzz| |1s’| |1s’UU 2s’ 2s’UU||

’’RHFRHF = = |1s|1sUU 2s 2sUU 2p 2pxx 2p 2pyy 2p 2pzz| |1s| |1sUU 2s 2sUU||

EEDMCDMC((’’RHFRHF) ) == EEDMCDMC((UHFUHF))

EEVMCVMC((’’RHFRHF) ) >> E EVMCVMC((RHFRHF) ) >> E EVMCVMC((UHFUHF))

Page 20: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Conventional wisdom on Conventional wisdom on

Node equivalent to a Node equivalent to a UHF UHF |f(r) g(r) 2p|f(r) g(r) 2p33| |1s | |1s 2s|2s|

EEDMCDMC((GVBGVB) ) == E EDMCDMC((’’’’RHFRHF))

GVBGVB = = |1s 2s 2p|1s 2s 2p33| |1s’ 2s’| - |1s’ 2s 2p| |1s’ 2s’| - |1s’ 2s 2p33| |1s 2s’| + | |1s 2s’| +

|1s’ 2s’ 2p |1s’ 2s’ 2p33| |1s 2s|- |1s 2s’ 2p| |1s 2s|- |1s 2s’ 2p33| |1s’ 2s|| |1s’ 2s|

Same NodeSame Node

Page 21: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Nitrogen AtomNitrogen Atom Param. Param. E corr. VMCE corr. VMC E E

corr. DMCcorr. DMC

Simple RHF (1 det)Simple RHF (1 det) 44 26.0%26.0%91.9%91.9%

Simple RHF (1 det)Simple RHF (1 det) 88 42.7%42.7%92.6%92.6%

Simple UHF (1 det)Simple UHF (1 det) 1111 41.2%41.2%92.3%92.3%

Simple GVB (4 det) Simple GVB (4 det) 1111 42.3%42.3%92.3%92.3%

Clementi-Roetti + JClementi-Roetti + J 2727 24.5%24.5%93.1% 93.1%

Is it worth to continue to add parametersIs it worth to continue to add parametersto the wave function?to the wave function?

Page 22: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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What to do?What to do?

Should we be happy with the “cancellation Should we be happy with the “cancellation of error”, and pursue it?of error”, and pursue it?

If so:If so: Is there the risk, in this case, that QMC Is there the risk, in this case, that QMC

becomes becomes Yet Another Computational ToolYet Another Computational Tool, and , and not particularly efficient nor reliable?not particularly efficient nor reliable?

VMC seems to be much more VMC seems to be much more robustrobust, , easy to easy to “advertise”“advertise”

If not, and pursue If not, and pursue orthodox QMCorthodox QMC (no (no

pseudopotentials, no cancellation of errors, …)pseudopotentials, no cancellation of errors, …) , can we , can we avoid theavoid the curse of curse of TT ? ?

Page 23: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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The curse of the The curse of the

QMC currently relies on QMC currently relies on TT(R)(R)

Walter Kohn in its Nobel lecture Walter Kohn in its Nobel lecture (R.M.P. (R.M.P. 7171, 1253 , 1253

(1999))(1999)) “discredited” the wave function as a “discredited” the wave function as a non non legitimate conceptlegitimate concept when when NN (number of (number of electrons) is largeelectrons) is large

1033 ppM N 1033 ppM N

pp = parameters per variable = parameters per variable

MM = total parameters needed = total parameters needed

For For MM=10=1099 and and pp=3=3 NN=6=6

The Exponential WallThe Exponential WallThe Exponential WallThe Exponential Wall

Page 24: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Convergence to the exact Convergence to the exact We must include the correct analytical structureWe must include the correct analytical structure

Cusps:Cusps:2

1)0( 1212

rr Zrr 1)0(

3-body coalescence and logarithmic terms:3-body coalescence and logarithmic terms:

QMC OKQMC OK

QMC OKQMC OK

Tails:Tails:Often neglectedOften neglected

Page 25: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Asymptotic behavior of Asymptotic behavior of

1221

22

21

1)

11()(

2

1

rrrZH

1221

22

21

1)

11()(

2

1

rrrZH

21

22

21

1)(

2

12

r

Z

r

ZH

r

21

22

21

1)(

2

12

r

Z

r

ZH

r

Example with 2-e atomsExample with 2-e atoms

IE2 IE222 1/)1(

210 )( rZr

err

22 1/)1(

210 )( rZr

err

)( 10 r )( 10 r is the solution of the 1 electron problemis the solution of the 1 electron problem

Page 26: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Asymptotic behavior of Asymptotic behavior of

)()()( 1221 rJrr )()()( 1221 rJrr The usual formThe usual form

)()()(

)()()(

2011

2102

rrr

rrr

)()()(

)()()(

2011

2102

rrr

rrr

does does notnot satisfy the asymptotic conditions satisfy the asymptotic conditions

)())()()()(( 121221 rJrrrr )())()()()(( 121221 rJrrrr

A closed shell determinant has the A closed shell determinant has the wrongwrong structure structure

Page 27: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Asymptotic behavior of Asymptotic behavior of

),...2()())(1( 101

11

/21

11110

1111

NYerOrcr Nml

brar

N

r ),...2()())(1( 101

11

/21

11110

1111

NYerOrcr Nml

brar

N

r In generalIn general

Recursively, fixing the cusps, and setting the right symmetry…Recursively, fixing the cusps, and setting the right symmetry…

UNN eNfffA ))()...2()1((ˆ

21 UNN eNfffA ))()...2()1((ˆ

21

Each electron has its own orbital, Each electron has its own orbital, Multideterminant (GVB) Structure!Multideterminant (GVB) Structure!

Take 2N coupled electronsTake 2N coupled electrons )...)(( 434321212 N )...)(( 434321212 N

22NN determinants. Again an determinants. Again an exponential wallexponential wall

Page 28: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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PsH – Positronium PsH – Positronium HydrideHydride

A wave function with the correct asymptotic A wave function with the correct asymptotic conditions:conditions:

Bressanini and Morosi: JCP Bressanini and Morosi: JCP 119119, 7037 (2003), 7037 (2003)

)()()()()ˆ1(),2,1( 112 pp rgPsrfHPp )()()()()ˆ1(),2,1( 112 pp rgPsrfHPp

Page 29: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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We need new, and We need new, and differentdifferent, , ideasideas

Research is the process of going up alleys to see if Research is the process of going up alleys to see if they are blind.  they are blind. 

Marston BatesMarston Bates

Research is the process of going up alleys to see if Research is the process of going up alleys to see if they are blind.  they are blind. 

Marston BatesMarston Bates

Different representationsDifferent representations Different dimensionsDifferent dimensions Different equationsDifferent equations Different potentialDifferent potential Radically different algorithmsRadically different algorithms Different Different somethingsomething

Page 30: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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JustJust an example an example

Try a different representationTry a different representation Is Is somesome QMC in the momentum QMC in the momentum

representationrepresentation Possible ? And if so, is it:Possible ? And if so, is it: Practical ?Practical ? Useful/Advantageus ?Useful/Advantageus ? Eventually better than Eventually better than plain vanillaplain vanilla QMC ? QMC ? Better suited for some problems/systems ?Better suited for some problems/systems ? Less plagued by the usual problems ?Less plagued by the usual problems ?

Page 31: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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The other half of Quantum The other half of Quantum mechanicsmechanics

))((ˆ)( rFp ))((ˆ)( rFp The Schrodinger equation in the momentum representationThe Schrodinger equation in the momentum representation

pdpppVpm

pE )()(ˆ)2()()

2( 2/1

2

pdpppVpm

pE )()(ˆ)2()()

2( 2/1

2

SomeSome QMC (GFMC) should be possible, given the iterative form QMC (GFMC) should be possible, given the iterative form

OrOr write the imaginary time propagator in momentum space write the imaginary time propagator in momentum space

Page 32: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Better?Better? For coulomb systems:For coulomb systems:

2

2)

1(ˆ)(ˆ

jiij pprFpV

2

2)

1(ˆ)(ˆ

jiij pprFpV

There are There are NO cuspsNO cusps in momentum space. in momentum space. convergence should be fasterconvergence should be faster

Hydrogenic orbitals are Hydrogenic orbitals are simple rational functionssimple rational functions

222

2/15

1 )(

)8()(

Zp

Zps

222

2/15

1 )(

)8()(

Zp

Zps

Page 33: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Another Another (failed so far) (failed so far) exampleexample

Different dimensionality: HypernodesDifferent dimensionality: Hypernodes Given Given HH((RR) = ) = EE((RR)) build build

dimensionsNHHH 6)()( 21 RR dimensionsNHHH 6)()( 21 RR

)()()()( 2121 RRRR BFFBT )()()()( 2121 RRRR BFFBT

•Use the Use the HypernodeHypernode of of TT

• The hope was that it could be better than Fixed Node The hope was that it could be better than Fixed Node

Page 34: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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HypernodesHypernodes

Exact nodeExact node

Trial nodeTrial node

Fixed NodeFixed Node

Exact nodeExact node

Trial nodeTrial node

Fixed HyperNodeFixed HyperNode

The energy is still an upper boundThe energy is still an upper bound Unfortunately, it seems to recover exactly the FN Unfortunately, it seems to recover exactly the FN

energyenergy

0)( RT 0)( RTThe intuitive idea was that the system The intuitive idea was that the system couldcould correct correct the wrong fixed nodes, by exploring regions wherethe wrong fixed nodes, by exploring regions where

Page 35: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

Why is QMC not Why is QMC not used by used by

chemists?chemists?

A little A little intermezzointermezzo

Page 36: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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DMC Top 10 reasonsDMC Top 10 reasons 12. We need forces, dummy! 12. We need forces, dummy!

11. Try getting O11. Try getting O22 to bind at the variational level. to bind at the variational level.

10. How many graduate students lives have been lost optimizing 10. How many graduate students lives have been lost optimizing wavefunctions? wavefunctions?

9. It is hard to get 0.01 eV accuracy by throwing dice. 9. It is hard to get 0.01 eV accuracy by throwing dice. 8. Most chemical problems have more than 50 electrons. 8. Most chemical problems have more than 50 electrons. 7. Who thought LDA or HF pseudopotentials would be any good? 7. Who thought LDA or HF pseudopotentials would be any good? 6. How many spectra have you seen computed by QMC? 6. How many spectra have you seen computed by QMC? 5. QMC is only exact for energies. 5. QMC is only exact for energies. 4. Multiple determinants. We can't live with them, we can't live 4. Multiple determinants. We can't live with them, we can't live

without them. without them. 3. After all, electrons are fermions. 3. After all, electrons are fermions. 2. Electrons move. 2. Electrons move. 1. QMC isn't included in Gaussian 90. Who programs anyway? 1. QMC isn't included in Gaussian 90. Who programs anyway?

http://web.archive.org/web/20021019141714/http://web.archive.org/web/20021019141714/archive.ncsa.uiuc.edu/Apps/CMP/topten/topten.htmlarchive.ncsa.uiuc.edu/Apps/CMP/topten/topten.html

Page 37: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

37

Chemistry and Chemistry and MathematicsMathematics

“The underlying physical laws necessary for the mathematical theory of a large part of physics and the whole of chemistry are thus completely known, and the difficulty is only that the exact application of these equations leads to equations much too complicated to be soluble”

P.A.M. Dirac - 1929

“The underlying physical laws necessary for the mathematical theory of a large part of physics and the whole of chemistry are thus completely known, and the difficulty is only that the exact application of these equations leads to equations much too complicated to be soluble”

P.A.M. Dirac - 1929

"We are perhaps not far removed from the time, when we shall be able to submit the bulk of chemical phenomena to calculation”

Joseph Louis Gay-Lussac - 1808

"We are perhaps not far removed from the time, when we shall be able to submit the bulk of chemical phenomena to calculation”

Joseph Louis Gay-Lussac - 1808

Page 38: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

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Nature and MathematicsNature and Mathematics

“il Grande libro della Natura e’ scritto nel linguaggio della matematica, e non possiamo capirla se prima non ne capiamo i simboli“

Galileo Galilei

“il Grande libro della Natura e’ scritto nel linguaggio della matematica, e non possiamo capirla se prima non ne capiamo i simboli“

Galileo Galilei

Every attempt to employ mathematical methods in the study of chemical questions must be considered profoundly irrational and contrary to the spirit of chemistry… If mathematical analysis should ever hold a prominent place in chemistry – an aberration which is happily almost impossible – it would occasion a rapid and widespread degeneration of that science.

Auguste Compte

Every attempt to employ mathematical methods in the study of chemical questions must be considered profoundly irrational and contrary to the spirit of chemistry… If mathematical analysis should ever hold a prominent place in chemistry – an aberration which is happily almost impossible – it would occasion a rapid and widespread degeneration of that science.

Auguste Compte

Page 39: Is QMC delivering its early promises? Dario Bressanini QMCI Sardagna (Trento) 2006  Universita’ dell’Insubria,

39

A Quantum Chemistry A Quantum Chemistry ChartChart

J.PopleJ.Pople

The more accurate the calculations became, the The more accurate the calculations became, the more the concepts tended to vanish into thin air more the concepts tended to vanish into thin air (Robert Mulliken)(Robert Mulliken)

Orthodox QMCOrthodox QMC

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Chemical conceptsChemical concepts

Molecular structure and geometryMolecular structure and geometry Chemical bondChemical bond

Ionic-CovalentIonic-Covalent Singe, Double, TripleSinge, Double, Triple

ElectronegativityElectronegativity Oxidation numberOxidation number Atomic chargeAtomic charge Lone pairsLone pairs AromaticityAromaticity

C OO C OO

NOT DIRECTLY OBSERVABLESNOT DIRECTLY OBSERVABLESILL-DEFINED CONCEPTSILL-DEFINED CONCEPTS

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NodesNodes

Should we concentrate on Should we concentrate on nodes?nodes?

Checked on small systems: L, Be, HeChecked on small systems: L, Be, He22++. See also . See also

MitasMitas

Conjectures on nodesConjectures on nodes have higher symmetry than have higher symmetry than itself itself resemble simple functionsresemble simple functions the ground state has only 2 nodal volumesthe ground state has only 2 nodal volumes HF nodes are quite good: they “naturally” have HF nodes are quite good: they “naturally” have

these propertiesthese properties

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Avoided crossingsAvoided crossings

BeBe

ee-- gas gas

StadiumStadium

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Nodal topologyNodal topology

The conjecture The conjecture (which I believe is true)(which I believe is true) claims claims that there are only two nodal volumes in that there are only two nodal volumes in the fermion ground statethe fermion ground state

See, among others:See, among others: Ceperley Ceperley J.Stat.PhysJ.Stat.Phys 6363, 1237 (1991), 1237 (1991) Bressanini and coworkers. Bressanini and coworkers. JCPJCP 9797, 9200 (1992), 9200 (1992) Bressanini, Ceperley, Reynolds, “Bressanini, Ceperley, Reynolds, “What do we know about What do we know about

wave function nodes?wave function nodes?”, in ”, in Recent Advances in Quantum Recent Advances in Quantum Monte Carlo Methods IIMonte Carlo Methods II, ed. S. Rothstein, World , ed. S. Rothstein, World Scientfic (2001)Scientfic (2001)

Mitas and coworkers Mitas and coworkers PRBPRB 7272, 075131 (2005), 075131 (2005) Mitas Mitas PRL PRL 9696, 240402 (2006), 240402 (2006)

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Avoided nodal crossingAvoided nodal crossing

At a nodal crossing, At a nodal crossing, and and are zero are zero Avoided nodal crossing is the rule, not the Avoided nodal crossing is the rule, not the

exceptionexception Not (Not (yetyet) a proof...) a proof...

0

0

0

0variablesNwithN

eqsN

eq313

.3

.1

variablesNwithNeqsN

eq313

.3

.1

IfIf HFHF has 4 nodeshas 4 nodes HF HF has 2 nodes, with a properhas 2 nodes, with a proper

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He atom with noninteracting He atom with noninteracting electronselectrons

Sss 153 Sss 153

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Casual similarity ?Casual similarity ?

First unstable antisymmetric stretch orbit of semiclassical linear helium along with the symmetric Wannier orbit r1 = r2 and various equipotential lines

HeliumSss 121

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Superimposed Hylleraas node

Casual similarity ?Casual similarity ?

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How to How to directlydirectly improve improve nodes?nodes?

Fit to a functional form and optimize the Fit to a functional form and optimize the parameters parameters ((maybe for small systemsmaybe for small systems))

IFIF the topology is correct, use a coordinate the topology is correct, use a coordinate transformationtransformation

)(RR T )(RR T

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Coordinate transformationCoordinate transformation

Take a wave function with the correct nodal Take a wave function with the correct nodal topologytopology

)(RR T )(RR T

HF HF

Change the nodes with a coordinate Change the nodes with a coordinate transformation transformation (Linear? Feynman’s backflow ?) (Linear? Feynman’s backflow ?) preserving the topologypreserving the topology

Miller-Good transformationsMiller-Good transformations

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Feynman on simulating Feynman on simulating naturenature

Nature isn’t classical, dammit, and if you Nature isn’t classical, dammit, and if you want to make a simulation of Nature, you’d want to make a simulation of Nature, you’d better make it quantum mechanical, and better make it quantum mechanical, and by golly it’s a wonderful problem, because by golly it’s a wonderful problem, because it doesn’t look so easyit doesn’t look so easy””

Richard Feynman Richard Feynman 19811981

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A QMC song...A QMC song...

He deals the cards to find the answersHe deals the cards to find the answers

the sacredthe sacred geometry of chancegeometry of chance

thethe hidden lawhidden law of a probable outcomeof a probable outcome

the the numbersnumbers lead a dance lead a dance

Sting: Shape of my heartSting: Shape of my heart

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Think Different!Think Different!