Preheat oven to 350°F (180°C). Spray a 13 x 9-inch baking pan with cooking spray. Line pan with parchment paper, letting excess extend over sides of pan.: As the oven warms you will smell a faint warmth from the heating elements, which signals readiness; this consistent heat helps the batter rise evenly, setting the edges while allowing the center to stay chewy. A well greased, parchment lined pan prevents sticking and makes removal effortless, so don't skip that step. Common mistakes include not preheating fully, which can cause uneven baking and a dense center, and failing to line the pan, which can tear the bars when removed.
In a large bowl, whisk together brown sugar, melted butter, and vanilla for 30 seconds. Add eggs, one at a time, whisking until combined after each addition. Sprinkle baking powder onto mixture, and vigorously whisk until combined; repeat procedure with salt. Gently stir in graham cracker crumbs, flour, and 3/4 cup (127 grams) chocolate just until combined. (Do not overmix.) Spread batter into prepared pan.: The mixture will feel glossy and slightly thick after whisking, with the brown sugar dissolving into the butter to form a caramel scented base; this aroma is a good cue that you are on track. Adding eggs one at a time creates a smooth emulsion which helps the final texture. When you fold in the dry ingredients, you should see speckles of graham cracker crumbs and small streaks of flour disappear quickly; stop mixing as soon as the batter is homogeneous to avoid toughness. A frequent error is overmixing at this stage, which develops gluten and yields gummy bars.
Bake until top is browned and crackly, edges are set, and a wooden pick inserted in center comes out with a few moist crumbs, about 30 minutes. Increase oven temperature to broil. Sprinkle marshmallows and remaining chocolate onto blondie.: During baking you'll notice the surface developing a glossy, crackled sheen and the kitchen filling with a toasty, caramel aroma; those are indicators the sugars are caramelizing properly. The edges will firm first, pulling slightly away from the pan, while the center should wiggle a touch when nudged, leaving moist crumbs on a tester. This stage locks in chew while letting the top form a desirable snap. A typical pitfall is baking too long which dries the bars and removes the gooey center; rely on the wooden pick test rather than clock time alone.
Broil on top rack until chocolate is melted and marshmallows are toasted, about 30 seconds, checking every 10 seconds. Using a wooden pick, swirl marshmallows and chocolate on top, if desired. Let cool completely in pan on a wire rack. Using excess parchment as handles, remove from pan, and cut into bars. Store in an airtight container for up to 3 days.: The broiler step elevates the texture by quickly charring the marshmallow surface and melting the reserved chocolate , creating striations of glossy chocolate and toasted sugar. The scent will shift to a toasty, slightly smoky note that feels indulgent. Distribute the toppings evenly so each square gets a mix of toasted marshmallow and melted chocolate. One mistake to avoid is piling too many marshmallows in one spot, which can create overly gooey islands rather than an even toasted layer.
Broil on top rack until chocolate is melted and marshmallows are toasted, about 30 seconds, checking every 10 seconds. Using a wooden pick, swirl marshmallows and chocolate on top, if desired. Let cool completely in pan on a wire rack. Using excess parchment as handles, remove from pan, and cut into bars. Store in an airtight container for up to 3 days.: The broiler action is dramatic and fast; you'll hear slight crackles as the marshmallow surface browns and you will see the chocolate gloss melt into pools. Keep the oven door open or watch through the window, because the change happens quickly; checking every 10 seconds prevents burning. Swirling with a wooden pick creates marbled patterns and helps the toppings integrate with the top layer. Cooling fully firms the bars so they cut cleanly, and using the parchment helps you lift the whole slab without squishing it. A common error is cutting while warm, which leads to squashed pieces; patience pays off here.