Essence of the Projector Augmented Wave (PAW) Method used in QMAS

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ss o h Poo ugd Wv PW Mhod usd MS Mso Kohy sh Isu o Ubquous gy Dvs No Isu o dvd Idus S d hoogy Id Os J -ohy@s.go. No Isu o dvd Idus S & hoogy IS Ou o u. Psudo-Pos d Poos &. soo hoy: Wv Fuos xo Vus d Chg Dsy Dsbuo & 4. Fouo o o gy: K gy xhg- Coo gy gy d Coso Chg & 4 4. o Koh-Sh quo d o Fos 4 5. so by P-Wv Bss S 6. Sss so by Ns-M Sh 5 7. Sh o Ob oud-s o Suu P.. Böh PB 4 99 544 D. Vdb PB 4 99 789 P.. Böh PB 5 994 795 4. Kss d D. Joub PB59 999 758 5 O.. Ns d.m. M PB 985 78 Dd Fouo S PW No by MS ou No Isu o dvd Idus S & hoogy IS

Fus o Poo ugd Wv PW Mhod. h PW sh ws dvod by obg ds o sudo-o d -o FPW hods.. uy osodg o h o h FPW hod wh oz o oxo s d. u v wv uos wh u ods u obd. hus g d o os uy d wh.. y -wv bss ouos USPP Uso PP. Sooh sudo wv uos d wh u SCF ouos wh usu v gohs b uzd obd wh FF hqus. o os d sss sos sy obd by sovd wv uos d SCF os. hus g-s su ouos b od. 4. sby o sudo-os d oos o h ss s gud s USPP d h xo vus hg dsy d o gy gv by soo hoy. Phys qus sd h ugo gos u gv v g h PS -wv xsso by h -wv xsso oud o d gd sh wh hos h s gos gv by usu sudo-wv uos oud o usu FF sh. No Isu o dvd Idus S & hoogy IS Wv Fuos Poo ugd Wv PW d Usu Psudoo Shs V Wv Fuos PW Sh Co Wv Fuos Psudo-Wv Fuos Psudo-Po Sh Psudo-Po

Dvo o Og b Io Cods wh gh P y FON & MPI No-Cosvg PP Vso KMIKZ by M. Kohy S. d. u - PW Poo ugd Wv Vso MS uu Ms Suo by S. Ishbsh. u S. M. Kohy d K. u 4-. u. Mod. Su. M. S. g. 4 945 Ou o u. Psudo-Pos d Poos &. soo hoy: Wv Fuos xo Vus d Chg Dsy Dsbuo & 4. Fouo o o gy: K gy xhg- Coo gy gy d Coso Chg & 4 4. o Koh-Sh quo d o Fos 4 5. so by P-Wv Bss S 6. Sss so by Ns-M Sh 5 7. Sh o Ob oud-s o Suu P.. Böh PB 4 99 544 D. Vdb PB 4 99 789 P.. Böh PB 5 994 795 4. Kss d D. Joub PB59 999 758 5 O.. Ns d.m. M PB 985 78 Dd Fouo S PW No by MS ou No Isu o dvd Idus S & hoogy IS

No-Cosvg Psudo-Po v NCPP Usu So Fo s v P v v v Y Φ P Y >< Y -o o KS q. Φ Φ v v v Φ d : o gy o Φ v P o gu-mou Poo Oo o No-o PP Zo o > d Y Φ Cosuo o V so s o Psudo o Wv Fuos o Ssy h No-Cosvg Codos D... P4979494 v NCPP o h No Isu o dvd Idus S & hoogy IS Psudo-Pos PP & Poos No-Cosvg PP KB-Sb PP zd PP zd Sb PP d Uso Vdb PP NCPP Usu So Fo v v s P Y >< Y NCPP o h o o Cuos K- Byd KB Sb Fo o NCPP C Φ Y v v v s v o v P v o v v v o No Isu o dvd Idus S & hoogy IS No-o PP Zo o > v P gu-mou Poo Oo o v Y Φ Y > v < Y > / C < v Φ Y < ΦY > Isd h o go h Psudo Wv Poo Fuo s oxy Φ Y xssd s Φ Y hus Psudo o Wv KB Fuo o v V s vo v Φ Y V s v o Sd o PP K & Byd P489845 v s KB

Psudo-Pos PP & Poos No-Cosvg PP KB-Sb PP zd PP zd Sb PP d Uso Vdb PP zd PP by PS P Wvs wh { } Sd gy d Sovd wh } v v v { v s KB v v o Φ Y v v v { Φ Y o Sooh PS P Wvs whou Nods Dd wh } v o s o v v ΦY Poo v v > / < v > < v o Sg Poo o h o KS q. P Wvs Dd wh No Isu o dvd Idus S & hoogy IS Φ Φ ; Uboudd Ss b D wh Sooh Coo bw d PS d Fuos PB 4989 98 Psudo-Pos PP & Poos No-Cosvg PP KB-Sb PP zd PP zd Sb PP d Uso Vdb PP zd Sb PP oosd by Böh Böh PB 499544 { v { } } { τ τ Φ τ Y v v o v o } v v v v τ τ o v v Φ τy χ { } B [ ] χ < χ > χ [ B ] B Du < >< > Coss zd Sb PP v v s v > B < o P d PS P Wvs Dd wh Cosuo o h Poo Du o h P Wvs o Mu Poos o h No Isu o dvd Idus S & hoogy IS > B < No Nd o D V Igo wh -Shd y Ohogozo s so Possb

Psudo-Pos PP & Poos No-Cosvg PP KB-Sb PP zd PP zd Sb PP d Uso Vdb PP { } } } { P Wvs PS P Wvs d Poos vo v zd v { vo } Sb χ < NCPP: S o χ > [ B ] χ < o PP d > Poos o v > B < h o B o { xo o h No-Cosvg Codo USPP by Vdb q < > < > q Igo wh Vdb PB4 S q >< 99789 < S > S { vo B q zd gvu >< } Pob Iudg S q >< q. o o Psudo Wv Fuos No Isu o dvd Idus S & hoogy IS Psudo-Pos PP & Poos No-Cosvg PP KB-Sb PP zd PP zd Sb PP d Uso Vdb PP sby o NCPP: Sg os odud wh h No-Cosvg Codo ogh dvv o h d WF s u oud USPP: Voo o h No-Cosvg Codo Coso Chg ovs h sby ogh dvv s u oud d : Coso Chg Mu Poos o h Is h uy No Isu o dvd Idus S & hoogy IS

Psudo-Pos PP & Poos No-Cosvg PP KB-Sb PP zd PP zd Sb PP d Uso Vdb PP USPP & PW: Coo S o o PP & PS Ps d Poos x } { } v { o & PS } P Wvs d Poos o M { o τ τ v : o Sd Φ Y τ o PP χ { v } v B o < χ > [ B ] χ P Y τ < >< > -Shd y ohogozo s so ossb : { } } { gh: P Y τ Böh PB 5 994 795 No Isu o dvd Idus S & hoogy IS Psudo-Pos PP & Poos No-Cosvg PP KB-Sb PP zd PP zd Sb PP d Uso Vdb PP USPP & PW: S o o PP d Poos o h o & zd gvu Pob Iudg S P Wvs PS P Wvs Poos d o PP { τ τ Φ Y } { } vo { } τ vo v v χ { vo} v : o Sd B < χ > [ B ] χ o PP P Y τ -Shd y < >< > ohogozo s so ossb q < > < > S q >< < S > { v B q >< } S o q >< No Isu o dvd Idus S & hoogy IS quo o Sg Poy o o No-SCF Sd

Ou o u. Psudo-Pos d Poos &. soo hoy: Wv Fuos xo Vus d Chg Dsy Dsbuo & 4. Fouo o o gy: K gy xhg- Coo gy gy d Coso Chg & 4 4. o Koh-Sh quo d o Fos 4 5. so by P-Wv Bss S 6. Sss so by Ns-M Sh 5 7. Sh o Ob oud-s o Suu P.. Böh PB 4 99 544 D. Vdb PB 4 99 789 P.. Böh PB 5 994 795 4. Kss d D. Joub PB59 999 758 5 O.. Ns d.m. M PB 985 78 Dd Fouo S PW No by MS ou No Isu o dvd Idus S & hoogy IS soo hoy d PS P Wvs & Poos wh dus h o S { } { } { } τ τ Y V Wv Fuo o PS V Wv Fuo by h Poo : Idx o g S soo Oo soo hoy o xo Vu <> o o Bu Wv Fuo No Isu o dvd Idus S & hoogy IS Bu PS Wv Fuo Su o : h Poos o h o S Su o : h Poo Ps o h o S Poo Fuo

No Isu o dvd Idus S & hoogy IS soo hoy Poo o h soo hoy Oo xo Vu <> o o Poo Fuo Is hs h d d d s ox Coss F Fo No Isu o dvd Idus S & hoogy IS soo hoy o V Chg Dsy Dsbuo o soo hoy o Poo Fuo Isd h ugd Sh h o S houghou h C

Who S udg o gos o o o Sh o No Isu o dvd Idus S & hoogy IS Ou o u. Psudo-Pos d Poos &. soo hoy: Wv Fuos xo Vus d Chg Dsy Dsbuo & 4. Fouo o o gy: K gy xhg- Coo gy gy d Coso Chg & 4 4. o Koh-Sh quo d o Fos 4 5. so by P-Wv Bss S 6. Sss so by Ns-M Sh 5 7. Sh o Ob oud-s o Suu P.. Böh PB 4 99 544 D. Vdb PB 4 99 789 P.. Böh PB 5 994 795 4. Kss d D. Joub PB59 999 758 5 O.. Ns d.m. M PB 985 78 Dd Fouo S PW No by MS ou No Isu o dvd Idus S & hoogy IS

Fouo o o gy by soo hoy [ ] [ ] o z : ouy : o hg dsy soo hoy F xsso K gy : u Wv Fuo o z x : o hg dsy o u o o gy by u Wv Fuos d u Chgs Isd h o Sh No Isu o dvd Idus S & hoogy IS Fouo o o gy: gy z : Nu d Co Chg Dsy Psudzd Nu Co Chg z : & z z z d z d z z z z z : u V Chg Dsy : Coso Chg Dsy & Bu go : S Muo Mos z z z vs z : S Mo vs : S Muo Mos vs Dsy : S Muo Mos : No Mos ousd o Sh z o Sh No Isu o dvd Idus S & hoogy IS z

No Isu o dvd Idus S & hoogy IS Psudoo o Usd v Mos Muo S z z z z ]: [ : vs Who S udg o gos o Sh z No Isu o dvd Idus S & hoogy IS d d Fouo o o gy: gy Sh o sd o du Sh o ousd Mos No : o B Ms Igo sd o Sh os Ios og h os d Nu Poo F h s Cosod o h gy h gy

Fouo o o gy: gy d xhg-coo gy z z z z PP. U Z z z z z z z z z z z z z o os Ios og PS V Chgs og Ios d bw PS Chgs d Ios o o Ios og u V Chgs d bw u V Chg d Nu & Co Chgs sd o Sh Ios og PS Chgs d bw PS Chgs d Ios o PP sd o Sh xhg- Coo gy x x x x : Co Chg Dsy P Co Chg ou. : U: Io-Io os [ ] [ ] [ ] [ ] u o Chg PB69878 No Isu o dvd Idus S & hoogy IS : Fouo o o gy: F Fo o d d x[ ] [ [ ] ] v [ z] d U Zo [ ] gy [ ] v [ z ] d [ ] [ ] v [ ] z d x o Psudo V Wv Fuos d Chgs obd o Su o Cys x Igo houghou h Sys Igo sd h o Sh U : os Io og v Psudoo v [ [ Po Co z z Ios ] : Usd ] : u by os os Nu o d & : Su o h o S No Isu o dvd Idus S & hoogy IS

Fouo o o gy: Coso Chg u Chg Dsy d -h Mo o q Y d d Y d q g Usd Isd o u Dsy s osud so s o hv h s uo os wh h o s d wh ough soohss o FF No Isu o dvd Idus S & hoogy IS o g d F xsso Oy s Udd d : d P o : u Co g : Coso Fuo o Soohg Ou o u. Psudo-Pos d Poos &. soo hoy: Wv Fuos xo Vus d Chg Dsy Dsbuo & 4. Fouo o o gy: K gy xhg- Coo gy gy d Coso Chg & 4 4. o Koh-Sh quo d o Fos 4 5. so by P-Wv Bss S 6. Sss so by Ns-M Sh 5 7. Sh o Ob oud-s o Suu P.. Böh PB 4 99 544 D. Vdb PB 4 99 789 P.. Böh PB 5 994 795 4. Kss d D. Joub PB59 999 758 5 O.. Ns d.m. M PB 985 78 Dd Fouo S PW No by MS ou No Isu o dvd Idus S & hoogy IS

S o d Koh-Sh quo Oho-Noy Codo og Psudo Wv Fuos d Ov Oo S { S } q q [ ] do o o o d d 4π q o Oo o h PW o gy D D D [ z ] x[ D d ] Bu Sd o Psudo-Po D [ ] [ ] z x [ ] [ ] z x Sd Po by u V Chg sd h o Sh Sd o o Psudo-Po sd h o Sh D No Isu o dvd Idus S & hoogy IS d Koh-Sh quo S Bu h o S PW No V..6 No Isu o dvd Idus S & hoogy IS

No Isu o dvd Idus S & hoogy IS No Isu o dvd Idus S & hoogy IS

No Isu o dvd Idus S & hoogy IS No Isu o dvd Idus S & hoogy IS

No Isu o dvd Idus S & hoogy IS o d d F { } [ ] { } [ ] o Z U S o Fos: -Fy ho { } [ ] o Z U S ] [ d v F z d F q D D D F [ ] d F x x Η D d v D No Isu o dvd Idus S & hoogy IS PW No V..6

No Isu o dvd Idus S & hoogy IS No Isu o dvd Idus S & hoogy IS

No Isu o dvd Idus S & hoogy IS > < q α P Podu o P h Fuo Fos: xs Oh os ossb o o o v s v q o < q B s q g α o o o g g g o d g Sooh PS P Wvs Usg Sh Bss Fuos Couousy Cod o P Wvs Sd o o Psudo- Po Couousy Cod o Sd Po Usg P Co Chg sd So dus Couousy Cod o u Co Chg ousd h dus Coso Fuo Usg Sh Bss Fuos Codos o D h Cos Poos osud by PS P Wvs d Sd o PP No Isu o dvd Idus S & hoogy IS [ ] d V d d d d d P Podu o Cou h o s: d Msh Igo sd o Sh [ ] [ ] d z z d d d 4 M M M M d d d d d π d d ] [ P d Y : hs os h quo.

No Isu o dvd Idus S & hoogy IS P Podu o Cou h o s: d Msh Igo sd o Sh [ ] d V d d d d d [ ] [ ] d z z d P d Y : d d 4 M M M M d d d d d π d d 4 M M M M g d g d d q d d π d d ] [ hs os h oowg h-ys o gos. M M M M g g d g g d d q q d d ' d d 4 π No Isu o dvd Idus S & hoogy IS Ou o u. Psudo-Pos d Poos &. soo hoy: Wv Fuos xo Vus d Chg Dsy Dsbuo & 4. Fouo o o gy: K gy xhg- Coo gy gy d Coso Chg & 4 4. o Koh-Sh quo d o Fos 4 5. so by P-Wv Bss S 6. Sss so by Ns-M Sh 5 7. Sh o Ob oud-s o Suu P.. Böh PB 4 99 544 D. Vdb PB 4 99 789 P.. Böh PB 5 994 795 4. Kss d D. Joub PB59 999 758 5 O.. Ns d.m. M PB 985 78 Dd Fouo S PW No by MS ou

No Isu o dvd Idus S & hoogy IS o B.Z. { } s o. I.P so by P-Wv Bss S: Usg o h Syy d D D Y Y γ α β γ o ; ; ; s os!!!!! β β β β F d [ ] d s os!!!!!!!! β β β Poo Fuo -S Igo houghou Bou Zo B.Z. -S Igo Idub P I.P. B.Z. by Usg Syy. : oo Mx o Sy Nssy o o h Poo Sh os Y by S M.. os y hoy o gu Mou α βγ: u gs o oo o Sh os Y P oo P I B Z &.... No Isu o dvd Idus S & hoogy IS C Y P so by P-Wv Bss S: Wv Fuos d Poos P P Y P N Φ { } Φ Φ C C 4 d P Y π 4 d P Y π P Wv Bss Psudo Wv Fuo u Wv Fuo Boh Su o PS P Wvs Poo h o S Poo Su Cys Sys P-Wv xsso o h Poo Vou C C h Poso Vo o Vo o Vo : }: { }: { }: {

No Isu o dvd Idus S & hoogy IS ' o I.P. ; ; ; ; b b b b C C C C D D { } o I.P. o I.P. o B.Z. C Y g q so by P-Wv Bss S: Poo Fuo d Chg Dsy Dsbuo Poo Fuo o b b wh d o o by sd o S h o Poo } { : ; V Chg Dsy : oo Mx o h Sy Coso Chg Dsy Fou Coos No Isu o dvd Idus S & hoogy IS o I.P. C C C so by P-Wv Bss S: o gy d x x V d V o o o V d V [ ] [ ] [ ] d z x o x o V V o : Fou Coos : o quo Posso Fo V [ ] [ ] [ ] z x d o o o V V v V o: Usd o o PP - : Io-Io os gy

No Isu o dvd Idus S & hoogy IS V d d ; so by P-Wv Bss S: o s sd o Sh [ ] [ ] [ ] d z x [ ] [ ] [ ] z z z d d d [ ] [ ] [ ] z x d d d d d d d d d h d os hs y o go h 4 h os hs y o go h d os hs y o go No Isu o dvd Idus S & hoogy IS D D D d D so by P-Wv Bss S: o d Koh-Sh quo [ ] [ ] [ ] x z D [ ] [ ] [ ] [ ] [ ] [ ] x z x z d D } { q S Igo h Cys Su Igo sd h o Sh q Igo wh

Ou o u. Psudo-Pos d Poos &. soo hoy: Wv Fuos xo Vus d Chg Dsy Dsbuo & 4. Fouo o o gy: K gy xhg- Coo gy gy d Coso Chg & 4 4. o Koh-Sh quo d o Fos 4 5. so by P-Wv Bss S 6. Sss so by Ns-M Sh 5 7. Sh o Ob oud-s o Suu P.. Böh PB 4 99 544 D. Vdb PB 4 99 789 P.. Böh PB 5 994 795 4. Kss d D. Joub PB59 999 758 5 O.. Ns d.m. M PB 985 78 Dd Fouo S PW No by MS ou No Isu o dvd Idus S & hoogy IS Sss so P-Wv Bss xsso: us o Dv h xsso σ o Do o Sss so : C Vou : S so Uo Doo o h Cys by S so γ I αγ α β β I α β γ αγ β Ns & M PB 985 78 No Isu o dvd Idus S & hoogy IS

No Isu o dvd Idus S & hoogy IS [ ] [ ] γ γ β αγ β α. I.P o I.P. C C o Sss so P-Wv Bss o- S xsso x x x x µ µ.. 4 4 β α π π o x o o o : oo Mx o h Sy D Fo No Isu o dvd Idus S & hoogy IS o 4 d V V o o π β α { : d W V K x x o-o µ µ Sss so P-Wv Bss o- S xsso o x o o o V o: Usd o o PP d Ds gv PW No. W d V K : o s o o

Ou o u. Psudo-Pos d Poos &. soo hoy: Wv Fuos xo Vus d Chg Dsy Dsbuo & 4. Fouo o o gy: K gy xhg- Coo gy gy d Coso Chg & 4 4. o Koh-Sh quo d o Fos 4 5. so by P-Wv Bss S 6. Sss so by Ns-M Sh 5 7. Sh o Ob oud-s o Suu P.. Böh PB 4 99 544 D. Vdb PB 4 99 789 P.. Böh PB 5 994 795 4. Kss d D. Joub PB59 999 758 5 O.. Ns d.m. M PB 985 78 Dd Fouo S PW No by MS ou No Isu o dvd Idus S & hoogy IS Podu o Ob h o oud S by Iv Shs oud wh Chg Mxg Sh o Posos h C Judg o o gy Covg o Fos Iu Chg Dsy Sss Cuo Judg o SCF & Ch Mxg I Wv Fuos K Mxg Puy Mxg Ouu Chg Dsy Iv Ud o h Wv Fuo o Mz h xo Vu o sdu Bo Dvdso & Kosug goh MM-DIIS Coug- d SD C- Po. Subs Dgozo & Ud o Ous uss Bodg No Isu o dvd Idus S & hoogy IS

ow o Ob h o oud S y by Iv Shs F o [{ ϕ}] λ ϕ ϕ o F λϕ ϕ λϕ λ ϕ g ϕ ϕ ϕ F ϕ ϕ λ ϕ λ ϕ ϕ λ ϕ ϕ s ϕ λ ϕ s ϕ ϕ ϕ ϕ K λ ϕ ϕ Kg ϕ ϕ ϕ ϕ ϕ ϕ ϕ / ϕ < g o-gy Mzo DF M N w d o sdu M N w K: Podog -Shd Ohogozo Ss Ds Mhod Coug-d Mhod MM- DIIS Mhod Bo Dvdso Mhod Kosug Mhod. No Isu o dvd Idus S & hoogy IS Coso bw Ss Ds d Coug-d Shs d g λ ϕ ϕ ϕ γ Kg ϕ ϕ α Kg γ γ g g g g S C No Isu o dvd Idus S & hoogy IS

Coso bw Coug- d d MM-DIIS Shs Coug-d o Ss Ds Sh MM-DIIS Sh Puy Mzo o xo Vu. Ud by d - -λ α - α α α - α α Mzo o sdu: -λ. s Udd So s o Mz < >. No Isu o dvd Idus S & hoogy IS Coso bw Coug- d d MM-DIIS Shs Coug-d o Ss Ds Sh MM-DIIS Sh h Ss Covg o h S Boo S No x Ohogozo. x Ohogozo s ss. h S C Covg o N g S wh. No Nd o Fqu Ohogozo. h S b Udd Iddy h CPU. No Isu o dvd Idus S & hoogy IS

Bo Dvdso Sh & Kosug goh ϕ s λ ϕ s g N w N w ϕ ϕ ϕ ϕ ϕ { ϕ ϕ } { Subs Dgozo Bo Dvdso Sh Kosug goh C ϕ { ϕ } } No Isu o dvd Idus S & hoogy IS { ϕ ϕ ϕ ϕ M ϕ ϕ} { ϕ ϕ} M M M M Coso bw Coug-d d Ss Ds Shs SC Su M. Kohy MSMS 4 996 97 SC/ I No Isu o dvd Idus S & hoogy IS

Coso bw Coug-d d Bo Dvdso Shs Dd o h Ps o K Sh M. Kohy MSMS 4 996 97 SC/ Is No Isu o dvd Idus S & hoogy IS Chg Mxg Sh S- Coss Ios F o [{ ϕ}] λ ϕ ϕ F ϕ [ ] ϕ λ ϕ w Ξ Ξ w od o λϕ ϕ λϕ ϕ od od ou ou od ou od ou ou λ ϕ ϕ K Mxg Puy Mxg No Isu o dvd Idus S & hoogy IS

ϕ Pzo by MPI ϕ λ ϕ ϕ } ϕ < { ϕ N w N w N w ogn w ϕ ϕ ϕ ϕ ϕ ϕ ϕ / ϕ M N w s λ ϕ s g h Nod FF h Nod ϕ ϕ ϕ Idd Ud o h Wv Fuo h Nod Bu Nssy o Muu Ohogozo -Shd Ohogozo Nssy o g D Couo og Nods No Isu o dvd Idus S & hoogy IS Dvo o Og b Io Cods wh gh P y FON & MPI No-Cosvg PP Vso KMIKZ by M. Kohy S. d. u - PW Poo ugd Wv Vso MS uu Ms Suo by S. Ishbsh. u S. M. Kohy d K. u 4-. u. Mod. Su. M. S. g. 4 945

y o P Couo MM-DIIS: MSPW Vso SO 7-o C Nw95 84 os Cus Mh: I Xo 449 Nod o N/:.94% Nods: Id % 5.6% Nods: Id 5%.7% 4 Nods: Id.5% y : 99% α: 76% v o g Nubs o Nods P y s Vy ood. Fo N4 99% d α76% No Isu o dvd Idus S & hoogy IS