Nonsymmorphic Symmetry-Protected Band Crossings in a Square-Net Metal PtPb$_4$

Topological semimetals with symmetry-protected band crossings have emerged as a rich landscape to explore intriguing electronic phenomena. Nonsymmorphic symmetries in particular have been shown to play an important role in protecting the crossings along a line (rather than a point) in momentum space. Here we report experimental and theoretical evidence for Dirac nodal line crossings along the Brillouin zone boundaries in PtPb$_4$, arising from the nonsymmorphic symmetry of its crystal structure. Interestingly, while the nodal lines would remain gapless in the absence of spin-orbit coupling (SOC), the SOC in this case plays a detrimental role to topology by lifting the band degeneracy everywhere except at a set of isolated points. Nevertheless, the nodal line is observed to have a bandwidth much smaller than that found in density functional theory (DFT). Our findings reveal PtPb$_4$ to be a material system with narrow crossings approximately protected by non-symmorhpic crystalline symmetries.


I. ABSTRACT
Topological semimetals with symmetry-protected band crossings have emerged as a rich landscape to explore intriguing electronic phenomena. Nonsymmorphic symmetries in particular have been shown to play an important role in protecting the crossings along a line (rather than a point) in momentum space. Here we report experimental and theoretical evidence for Dirac nodal line crossings along the Brillouin zone boundaries in PtPb 4 , arising from the nonsymmorphic symmetry of its crystal structure. Interestingly, while the nodal lines would remain gapless in the absence of spin-orbit coupling (SOC), the SOC in this case plays a detrimental role to topology by lifting the band degeneracy everywhere except at a set of isolated points. Nevertheless, the nodal line is observed to have a bandwidth much smaller than that found in density functional theory (DFT). Our findings reveal PtPb 4 to be a material system with narrow crossings approximately protected by non-symmorhpic crystalline symmetries.

II. INTRODUCTION
Since the discovery of topological insulators more than a decade ago, the classification of quantum materials has undergone a revolution, where quantum materials are now categorized by their topological properties and associated symmetries [1][2][3][4][5][6][7][8][9][10]. This is epitomized by the study of topological semimetals (TSMs), which are 3-dimensional analogs to graphene where the bulk bands cross without opening an energy gap [11]. Crystalline symmetries, such as nonsymmorphic symmetry, can play a crucial role in protecting the band crossings along a continuous line or loop in momentum space in TSMs, yielding what is known as a nodal line semimetal (NLS). Nonsymmorphic symmetries combine a fractional lattice translation with either a mirror reflection (glide plane) or a rotation (screw axis), resulting in a band-folding with crossings at the Brillouin zone (BZ) boundaries that are protected against hybridization [12,13]. As long as the nonsymmorphic symmetry remains intact, these so-called essential band crossings are impervious to the presence of SOC [12][13][14]. If furthermore the degenerate bands only slightly disperse, one observes the symmetry-protected crossings of narrow bands, which when doped to the chemical potential may host correlated topological phases [15][16][17].
In contrast to the vast repository of materials with band crossings that are unprotected against SOC, there are only a handful of materials that realize nonsymmorphic symmetryprotected Dirac crossings. The search for nonsymmorphic topological materials has largely been guided by a work from Young and Kane [18], which demonstrated that two-dimensional square net motifs can generate Dirac nodes, when the square net is itself embedded in a unit cell that is twice as large and hence the two atoms in the unit cell are related by a glide plane. This blueprint has been followed in the case of ZrSiS, which has the nonsymmorphic space group P 4/nmm with Si occupying a square net. ARPES measurements on ZrSiS [19,20] and several isosructural compounds [21,22] have revealed nonsymmorphic symmetry-protected Dirac nodal lines with linear dispersions over more than 2 eV. Several years onward, ZrSiS and its structural analogs, whose electronic structure can be well captured by DFT, remain one of the few experimental manifestations of this class of topological materials [23,24].
Here we report the discovery of a nonsymmorphic symmetry protected topological semimetal displaying narrow bands along the BZ boundary, PtPb 4 . Distinct from a previous report on PtPb 4 crystals that exhibit a crystal structure consistent with space group Ccce [25], our post-annealed crystals exhibit tetragonal symmetry of the space group P 4/nbm. Our ARPES measurements reveal a set of nearly flat degenerate bands along the BZ boundary that appear to originate from the linear crossing of two bulk bands along the orthogonal momentum direction. Careful analysis of space group symmetries and their representations in the BZ shows that the band degeneracies along the BZ boundary originate from nonsymmorphic symmetry elements. Surprisingly, despite the large SOC expected from the heavy elements constituting PtPb 4 , the observed splitting of the bands is much smaller than predicted by ab initio calculations based on DFT. By comparing our ARPES measured bands with those from both DFT and dynamic mean field theory (DMFT) calculations [26][27][28][29], we further explore the role of electron correlation effects on the band details. PtPb 4 therefore is one of the few reported nonsymmorphic symmetry-protected TSMs outside the well-known ZrSiS family that exhibits narrow bands in the presence of non-trivial topology.

III. RESULTS AND DISCUSSION
A. Crystal structure and nonsymmorphic symmetry PtPb 4 , grown by the metallic flux method, forms in the tetragonal space group 125 (P 4/nbm) with lattice parameters a = 6.66Å and c = 5.978Å [30]. No structural phase transitions are found down to 2 K. A recent study on PtPb 4 suggested that this material is polymorphic, with similar formation energies for tetragonal and orthorhombic structures [25].
In our study, we determined that extensive post-growth annealing (described in Supplementary Note 1 and Note 2) was critical to obtaining a single phase tetragonal material. The tetragonal crystal structure of PtPb 4 consists of staggered layers of Pt and Pb, as seen in Fig. 1a. Two layers of Pb (gold) are sandwiched between consecutive layers of Pt (blue). Each Pb layer forms a Shastry-Sutherland lattice while a square net is formed by each Pt layer. This crystal structure exhibits nonsymmorphic symmetry through a glide-mirror operation, as illustrated in Fig. 1a. For the Pb in site A, a mirror reflection operation m z brings it to site B, which is not an allowed position in the structure. An additional fractional translation is needed (t : 1 2 , 1 2 , 0) to bring it to the allowed atomic site C. We note that PtPb 4 is structurally similar but not isostructural with PtSn 4 , which has been reported to exhibit Dirac nodal arc surface states [31], features that are apparently unrelated to the nonsymmorphic symmetry. We note that the intensity of the FS appears to indicate C 4 symmetry-breaking, which has also been reported by a laser-ARPES work [25]. However, we caution that since our polarization used is along the k x direction, the photoemission matrix elements also break C 4 symmetry, which prevent us from concluding whether the intrinsic electronic structure breaks C 4 symmetry. However, our powder x-ray diffraction measurements show no evidence of C 2 symmetry in our annealed crystals, suggesting that our bulk bands should exhibit C 4 symmetry. Notably, at a binding energy of 0.6 eV below the Fermi level (E F ), an intense grid-like feature appears along the lines that coincide with the boundaries of the BZ, as evident in the measured constant energy contour (Fig. 1c), reminiscent of the nonsymmorphic symmetry-protected features originally predicted by Young and Kane [18]. To see the band dispersions that give rise to this feature, we show the spectral images measured along the high symmetry directions of the BZ (Fig. 1d). First, along the Γ-X direction, a series of electron bands appear. Closer to the X point, we also observe two highly dispersive bands that meet at the X point. In contrast to the Γ-X direction, intensity from dispersions along the X-M direction are mostly confined within the energy window of −0.9 eV to −0.3 eV, where a set of largely flat bands appear, in particular, near −0.6 eV. These are the bands that give rise to the grid-like features outlining the BZ boundaries in the constant energy contour in Fig. 1c.
To identify whether the crossing is of bulk or surface nature, we carried out a photon energy dependence study for probing along the k z direction. A number of features in the constant energy contour taken at -0.6eV are shown to be periodic, and therefore identified as bulk bands (Fig. 1f). In particular, we find that the bands giving rise to the Dirac crossing at the BZ boundary exhibit different band velocities at k z =0 and π. This is illustrated in a cut near the X-R direction (Fig. 1g), where the Dirac dispersion is observed to be periodic along k z , indicating that it is bulk in nature. The grid-like feature this band forms in the constant energy contour indeed appears at all BZ boundaries, respecting the bulk C 4 symmetry.
Moreover, we also note a clear k z broadening effect for this band, seen in the broadened intensity where this band disperses across k z . This is an effective integration along k z due to the low resolution of the photoemission process in the out-of-plane direction [32]. We carried out semi-infinite slab calculations using DFT based on the Green's function method [33].
The resulting calculated FS, shown in the bottom right panel of Fig. 1b, reproduces the series of pockets centered at Γ seen in ARPES. At −0.6 eV, large pockets centered at Γ are also reproduced. Importantly, this calculation also reproduces the grid like outline of the BZ boundaries (bottom right panel in Fig. 1c). Due to the strong k z broadening observed, we compared the measured dispersions with the calculated k z integrated band dispersions along Γ-X. Largely dispersive features appear to qualitatively match those seen in the ARPES data. Along the high-symmetry X-M line, a number of bands appear in the energy range centered at −0.6 eV, which likely correspond to the bands giving rise to the grid-like feature in the constant energy contour. However, the calculated dispersions along the X-M line span a larger energy window than what is observed experimentally, indicating a subtle mechanism that is not captured by the DFT calculations.
In order to shed more light on the nature of the band crossings along the edges of the BZ, we analyze in detail the measured band dispersions along and perpendicular to the X-M BZ boundary (Fig. 2). To better visualize the band dispersions, we plot the 2D curvature of the spectral image along the Γ-X-M path in Fig. 2a. The pair of bands highlighted in red in Fig. 2a disperse along Γ-X to meet at a degenerate point at X, then remain nearly degenerate across the X-M edge of the zone. To see this, we examine a series of ten cuts (C1 to C10) perpendicular to the X-M direction (Fig. 2b). From C1, the linear Dirac crossing can be clearly observed near −0.6 eV. As we move away from the X point, this Dirac crossing remains centered at nearly the same energy. In C6 and C7, a gap is resolved at the Dirac point, and subsequently closes approaching the M point (C8 to C10), although a small gap may persist along the cut beyond our experimental resolution. We note that the bandwidth of this nodal line is less than 0.2 eV along the BZ boundary direction. In addition, another set of nearly degenerate bands can be observed near −0.9 eV, as marked in yellow on cuts C5 to C8. The crossing points of these bands are also indicated for clarity by yellow dots along the X-M line in Fig. 2a. We therefore conclude that what appears to be a nearly flat grid-like feature at −0.6 eV in the ARPES data is actually a set of two bands that cross or nearly cross along the X-M line at the BZ edge. This can also be seen in constant energy contours. As shown in Fig. 2c, a line segment lining the BZ boundary at −0.6 eV evolves into two separate features both above and below in energy due to the Dirac bands dispersing away from the nodal crossing.

C. Symmetry analysis and first-principle calculations
The intriguing features in both the measured and calculated band dispersions prompted us to examine these findings in the context of the nonsymmorphic symmetry of PtPb 4 . The glide mirror symmetries of the space group can be represented byĝ x = {m 010 | 1 2 , 0, 0} and g z = {m 001 | 1 2 , 1 2 , 0} (Note that these operations are defined with respect to the standard primitive cell for space group 125, which has its origin shifted by (0, 1 /4, 0) with respect to Fig. 1(a)). As these operations are orthogonal to each other (anticommuting), in the absence of SOC, the bands ψ + and ψ − =ĝ x ψ + carry opposite eigenvalues ofĝ z and are hence degenerate along the BZ boundary (Fig. 3a). With the inclusion of SOC, a gap opens along the BZ boundary except at the highest symmetry points, owing to the breaking of the anti-commutation relation betweenĝ x andĝ z (Fig. 3b). With SOC present, the double space-group operation requiresĝ x andĝ z to commute in spin space as well. Thus, instead of the anti-commutator {ĝ x ,ĝ z } = 0, one has the commuting relation [ĝ x ,ĝ z ] = 0 under SOC.
As a result, the action of the glide plane on a band ψ − =ĝ x ψ + is no longer degenerate with ψ + as they now carry the sameĝ z eigenvalue. Consequently, every band along X-M (and the equivalent direction R-A) is only degenerate with its Kramers' pair, except at the high symmetry points at k y = 0 (X) or π (M-point), where the four-fold degeneracy remains due to the presence of both time reversalT and parityP symmetries. We therefore find that, in the absence of SOC, the nonsymmorphic symmetry in PtPb 4 must protect the band degeneracy along the BZ boundary, similar to earlier theoretical reports on nonsymmorphic structures [13,34]. However, the presence of SOC lifts the degeneracy except at a set of isolated points. The nonsymmorhpic symmetry of the crystal could also explain the strong intensity asymmetry of the Dirac dispersions about the BZ boundary ( Fig. 1h-i), where the glide mirror symmetry switches the parity of the orbital symmetries, as has been observed in the iron pnictides [35].
To demonstrate this protected degeneracy revealed in the above symmetry analysis, we first carried out DFT calculations without SOC (Fig. 4c). Next, we consider the effect of SOC, which is expected to be substantial in PtPb 4 . When SOC is included into the DFT+U calculation (Fig. 4c), the degeneracy between each pair of bands along the R-A (and X-M) line is lifted. Nevertheless, a fourfold degeneracy is indeed retained at the high-symmetry R and A points (as well as X and M), as predicted to be protected by the nonsymmorphic symmetry. Although the above symmetry analysis only guarantees the band crossings at isolated points (X, M, R, A) on the zone boundary, it does not preclude accidental crossings of the bands between these points on the R-A (X-M) line.
Indeed as seen in calculations with SOC, accidental crossings between pairs of bands do happen and are marked by circles in Fig. 4c. We emphasize that these crossings are not symmetry-enforced -they are accidental -but once the bands cross, the screw rotation s 2y = {2 010 | 1 2 , 0, 0} protects the crossing from being gapped (see the Supplementary Note 4 for more details).
While the DFT+U calculations show qualitative agreement with our experimental observations, we note that some inconsistencies remain. One example is the bandwidth of Dirac nodal lines along the BZ boundary, which remain well above that observed experimentally (0.2 eV). Another example is the band highlighted in green along X/R to M/A in the measured dispersions shown in Fig. 4b, which also has a larger bandwidth and remains above E F along R-A cut (Fig. 4c), in contrast to the data. We note that while the k z broadening effect could possibly explain the dispersion of this band towards E F (see Supplementary Note 3 and Note 6), one still needs a mechanism to reduce the bandwidth towards that experimentally observed. We then examine factors missing in DFT and DFT + U calculations. One possibility is the dynamic correlation effects, which we probe with DMFT by calculating the energy-momentum-dependent spectral function (see Supplementary Note 7 for details). From the orbital-resolved density of states (Fig. 4d), the Pt d-orbitals and the Pb p-orbitals both contribute significantly near E F . We therefore examine the effect of dynamic correlations in each. We study the effect of the on-site Coulomb interactions (U d ) of the Pt d-orbitals and find that an increase from 3 eV to 8 eV causes the reduction of the bandwidth of the green-highlighted band along Z-R-A, resulting in the portion along R-A crossing E F (Supplementary Figure 8). This demonstrates an overall systematic improvement with the experimental observations from DFT and DFT+U, as captured by all of the extracted quantities in Fig. 4e. Similar theoretical experiment on U P b p (while smaller than U P t d ) also shows a positive modification of this band, as demonstrated by the comparison in Fig. 4e. In particular, the dispersive hole band shows an improvement over the DFT+U results in terms of its agreement with the experimental observation. However, the bandwidth of the nodal lines still remain sizeable, indicating that other effects such as orbital-dependent correlations may need to be further explored. We note that a recent optical study also reported electron correlation effects that flatten the nodal lines in ZrSiS [36].

D. Band topology
Lastly, we note that PtPb 4 is also classified as a strong topological insulator based on the symmetry indicator and topological quantum chemistry classification [6-10, 37, 38] in Despite the lack of a bulk gap in this case, the k z = 0 and k z = π planes still preserve time-reversal symmetry and are fully gaped. Thus, we have two 2D topological invariants Z 2 validly defined for these two planes. Z 2 = 1(0) at k z = 0(π) planes, indicating that the semimetal phase of PtPb 4 at U = 3 eV is topological as well. We conclude that the static interaction included in the DFT + U calculation triggers a phase transition between a topological insulating state and a topological semimetal state in PtPb 4 . High resolution synchrotron powder X-ray diffraction data (λ = 0.457861Å) were collected up to 2θ = 28 • at the 11-BM beamline at the Advanced Photon Source (APS) of Argonne National Laboratory. Discrete detectors collected data points every 0.001 • and a scan speed of 0.1 • sec −1 at room temperature. Rietveld refinement, carried out with TOPAS-Academic software, confirms that PtPb 4 crystallizes in the tetragonal P 4/nbm space group (125), as previously determined [30]. Attempts to refine the model in other space groups previously used for PtSn 4 such as Aba2 [39] or Ccca [40] cannot account for the reflections. We also evaluated the (1, 1, l /2) positions and do not see additional reflections, in contrast to the report in Ref. [25]. The samples were cleaved in-situ and kept in ultra high vacuum with a base pressure lower than 4 × 10 −11 torr during measurements.

C. First principle calculations
The first-principle calculations in this work were carried out by employing the Vienna Ab initio Simulation Package (VASP) with the projector augmented wave (PAW) method [41].
We used the generalized gradient approximation (GGA), as implemented in the Perdew-Burke-Ernzerhof (PBE) functional [42]. The cutoff parameter for the wave functions was set to be 500 eV. The Brillouin Zone (BZ) was sampled by the gamma-centered method with a k-mesh 9 × 9 × 9. The surface states and the Wilson loop were calculated by using our in-house code TMC (Library for Topological Material Calculations) with the iterative Green's function approach [33] based on the maximally localized Wannier functions [43] obtained through the VASP2WANNIER90 [44]. The DMFT full charge self-consistency with DFT was achieved by employing the embedded-DMFT package [45]. We first obtain the band structure using DFT with the PBE exchange correlation functional in Wien2k. The impurity problem was solved with continuous-time quantum Monte Carlo method [46][47][48][49].

V. DATA AVAILABILITY
The data that support the findings of this study are available from the corresponding author upon reasonable request.

VIII. COMPETING INTERESTS
The authors declare no competing interests.